CN114296315A - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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Publication number
CN114296315A
CN114296315A CN202111430178.6A CN202111430178A CN114296315A CN 114296315 A CN114296315 A CN 114296315A CN 202111430178 A CN202111430178 A CN 202111430178A CN 114296315 A CN114296315 A CN 114296315A
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CN
China
Prior art keywords
photosensitive resin
resin composition
mass
meth
group
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Pending
Application number
CN202111430178.6A
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Chinese (zh)
Inventor
内藤一也
山田有里
小坂隼也
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Asahi Kasei Corp
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Asahi Kasei Corp
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Publication of CN114296315A publication Critical patent/CN114296315A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1063—Esters of polycondensation macromers of alcohol terminated polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polymerisation Methods In General (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A photosensitive resin composition comprising an alkali-soluble polymer, a compound having an ethylenic double bond, and a photopolymerization initiator, wherein a photosensitive resin layer formed from the photosensitive resin composition is laminated at a thickness of 25 μm on a copper-clad laminate in which a copper foil having a thickness of 18 μm is laminated, a cured resist pattern is formed by light irradiation and development treatment in a pattern form having a line/space of 50 μm/30 μm, copper etching treatment is performed at 50 ℃ for 55 seconds, and then the bottom width of a copper wire pattern obtained by removing the cured resist pattern is 38 μm or more.

Description

Photosensitive resin composition
The present application is a divisional application of the present application having an application date of 2016, 9/7, an application number of 201680052525.7, and a name of the present application being a photosensitive resin composition.
Technical Field
< field of the invention
The first embodiment of the present invention relates to a photosensitive resin composition.
< field of the invention in accordance with the second embodiment >
The second embodiment of the present invention relates to a photosensitive resin composition and the like.
< field of the invention in the third embodiment >
The third embodiment of the present invention relates to a photosensitive resin composition and the like.
< field of the invention in accordance with the fourth embodiment >
The fourth embodiment of the present invention relates to a photosensitive resin composition.
Background
< background art according to the first embodiment of the present invention >
Printed circuit boards are typically manufactured by photolithography. The photolithography method is a method of forming a layer made of a photosensitive resin composition on a substrate, pattern-exposing and developing the coating film to form a resist pattern, forming a conductor pattern by etching or plating, and removing the resist pattern on the substrate to form a desired wiring pattern on the substrate.
In the photolithography method, when a photosensitive resin composition layer is formed on a substrate, there are known: a method of removing the solvent after coating the composition solution; and a method in which a photosensitive element or a dry film resist formed by laminating a support and a photosensitive resin composition layer is laminated on a substrate, and then the support is peeled off.
In the manufacture of printed wiring boards, photosensitive elements are often used. There are many known examples of a method for forming a wiring pattern using the photosensitive element and a photosensitive resin composition suitable for the method.
For example, patent document 1 discloses a method for easily forming a copper wiring pattern having a good cross-sectional shape, and a photosensitive resin composition used in the method;
patent document 2 discloses a photosensitive resin composition containing a specific addition polymerizable monomer having an ethylenic double bond.
However, in recent years, due to the high density of printed wiring boards, the number of substrates tends to be increased. In the multilayer substrate, a through hole is provided for conducting between the substrates stacked up and down. When a wiring pattern is formed by photolithography on a substrate having a through hole used in a multilayer substrate, a resist film (a cap film) formed on the through hole is required to have properties (resistance to cap film cracking or capping property) that are not damaged by a spray pressure during development, washing, or the like.
In this regard, patent document 3 discloses a photosensitive resin composition containing a binder polymer having a small degree of dispersion (Mw/Mn), a photopolymerizable compound, and an acridine compound, and describes that a resist film having excellent pinhole characteristics can be formed using the composition.
< background art according to a second embodiment of the present invention >
Printed circuit boards are typically manufactured by photolithography. The photolithography method is a method of forming a coating film including a layer formed of a photosensitive resin composition on a substrate, pattern-exposing and developing the coating film to form a resist pattern, forming a conductor pattern by etching or plating treatment, and removing the resist pattern on the substrate to form a desired wiring pattern on the substrate.
In the photolithography method, when a photosensitive resin layer is formed on a substrate, there are known: a method of removing the solvent after coating the composition solution; and a method in which a photosensitive element or a dry film resist formed by laminating a support and a photosensitive resin layer is laminated on a substrate, and then the support is peeled off.
In the manufacture of printed wiring boards, photosensitive elements are often used. There are many known examples of a method for forming a wiring pattern using the photosensitive element and a photosensitive resin composition suitable for the method.
For example, patent document 1 discloses a method for easily forming a copper wiring pattern having a good cross-sectional shape and a photosensitive resin composition used in the method, and patent document 4 discloses a photosensitive resin composition containing a specific addition polymerizable monomer having an ethylenic double bond.
< background art according to a third embodiment of the present invention >
Printed circuit boards have been conventionally manufactured by photolithography. In the photolithography method, first, a photosensitive resin composition layer stacked on a substrate is pattern-exposed. The exposed portion of the photosensitive resin composition is polymerized and cured (negative type) or becomes soluble in a developer (positive type). Next, the unexposed portions (negative type) or the exposed portions (positive type) are removed with a developer to form a resist pattern on the substrate. Further, after the conductor pattern is formed by etching or plating, the resist pattern is peeled off and removed from the substrate. Through these steps, a conductor pattern is formed on the substrate.
In general, photolithography uses either a method of applying a solution of a photosensitive resin composition onto a substrate and drying the solution, or a method of laminating a photosensitive resin composition layer of a dry film resist (a photosensitive resin laminate in which a photosensitive resin composition layer is laminated on a support) onto a substrate. The latter is often used in the manufacture of printed circuit boards.
With the recent miniaturization of wiring intervals in printed wiring boards, various characteristics are required for dry film resists. As the wiring pitch is reduced, the thickness of the dry film resist tends to be reduced, but strong hole-covering properties are still required to protect the through hole on the substrate.
In addition, when the resist pattern is developed, the resist component is eluted between the patterns due to the moisture remaining between the patterns, and a water-remaining short-circuit failure occurs. In order to reduce the water residual short circuit failure, it is necessary to increase the hydrophobicity of the cured resist.
In order to improve the characteristics of resists, various photosensitive resin compositions have been proposed (patent documents 5 and 6).
< background art according to a fourth embodiment of the present invention >
Printed circuit boards are typically manufactured by photolithography. The photolithography method is a method of forming a layer made of a photosensitive resin composition on a substrate, pattern-exposing and developing the coating film to form a resist pattern, forming a conductor pattern by etching or plating, and removing the resist pattern on the substrate to form a desired wiring pattern on the substrate.
In the photolithography method, when a photosensitive resin layer is formed on a substrate, a method of removing a solvent after applying a composition solution; and a method of laminating a photosensitive element or a dry film resist, which is obtained by laminating a support and a photosensitive resin layer, on a substrate and then peeling off the support.
In the manufacture of printed wiring boards, photosensitive elements are often used. A method for forming a wiring pattern using the photosensitive element and a photosensitive resin composition suitable for the method are known (patent documents 1 and 2). Patent document 1 describes a conventional method for forming a copper wiring pattern having a good cross-sectional shape, and a photosensitive resin composition used for the method. Patent document 2 describes a photosensitive resin composition containing a specific addition polymerizable monomer having an ethylenically unsaturated bond.
With the recent miniaturization of wiring intervals in printed wiring boards, characteristics such as resolution are required for dry film resists. For example, various photosensitive resin compositions have been proposed for improving the characteristics of resist patterns (patent documents 5 and 6).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-233769
Patent document 2: international publication No. 2009/022724
Patent document 3: japanese patent laid-open publication No. 2013-109321
Patent document 4: japanese laid-open patent publication No. 2015-60120
Patent document 5: international publication No. 2015/098870
Patent document 6: japanese patent laid-open publication No. 2014-048340
Disclosure of Invention
Problems to be solved by the invention
< problem to be solved by the first embodiment of the present invention >
In recent years, circuit boards are generally manufactured by a line in which substrates are sequentially processed while being conveyed in a fixed direction. Here, when a conductor pattern such as a line/space pattern is formed on a substrate, the conductor lines may be parallel (MD-direction line), perpendicular (TD-direction line), or oblique with respect to the substrate conveyance direction. When a conductor pattern of a line/space pattern is formed by a flow line using a conventional resist material, the wiring widths of the lines in the MD direction and those of the lines in the TD direction are different, and a so-called longitudinal/lateral difference in wiring width occurs. In many cases, the MD direction lines are more easily eroded by the etching solution than the TD direction lines, and therefore the amount of etching increases, and the wiring width tends to become narrow. In order to form a fine conductor pattern by a flow line, it is preferable to reduce such a difference in wiring width between the MD-direction wiring and the TD-direction wiring.
However, in the conventional techniques represented by the above patent documents 1 to 3, no studies have been made from such a viewpoint, and a resist material for reducing the aspect difference of the wiring width has not yet been known.
The first embodiment of the present invention has been made in view of the above situation. Accordingly, an object of the first embodiment of the present invention is to provide a resist material in which a longitudinal/lateral difference in wiring width is suppressed when a fine conductor pattern is formed in a flow line.
< problem to be solved by the second embodiment of the present invention >
In order to form a resist pattern using the photosensitive resin composition, a developing process is performed. In this developing step, the composition in the exposed region is dissolved and removed in the case of a positive composition and the composition in the exposed region is dissolved and removed in the case of a negative composition, respectively, to form a resist pattern. In this developing step, the composition in the unnecessary region is not entirely "dissolved" in the developer, but is dispersed in the developer with at least a part thereof remaining in an insoluble state, and is removed from the substrate. Therefore, the amount of unnecessary substances in the developer increases every time the developing process is repeated, and finally insoluble components having poor dispersibility sometimes form aggregates. Such aggregates may remain attached to a substrate to be developed later, and may cause a short-circuit failure or the like.
Therefore, from the viewpoint of improving the yield of products in the development step and reducing the production cost of printed wiring boards, it is strongly desired that the photosensitive resin composition used has good dispersibility of the developer.
In recent years, demands for miniaturization and miniaturization of printed wiring boards have been increasing. Therefore, the photosensitive resin composition used for forming the printed wiring board is also required to be capable of forming a fine pattern. Here, since the minimum size of the pattern formed on the substrate depends on the exposure wavelength, it is theoretically not much difficult to form a miniaturized pattern by exposure using a photosensitive polymerization initiator corresponding to the exposure wavelength used. However, a fine pattern formed by exposure to light having a size of, for example, several tens of μm or less may peel off from a substrate in a subsequent step such as a development step, and as a result, miniaturization of a printed wiring board is limited.
Therefore, in order to form a fine printed wiring board, a photosensitive resin composition having high adhesion of a fine pattern is required.
However, the photosensitive resin compositions described in patent documents 1 and 4 cannot satisfy the current severe requirements in terms of both development dispersibility and adhesion of fine patterns, and there is room for improvement in this field.
The second embodiment of the present invention has been made in view of such a situation.
Accordingly, an object of the second embodiment of the present invention is to provide a novel photosensitive material having performance generally required for a photosensitive material such as resolution at a high level and excellent development dispersibility and adhesion of a fine pattern.
< problem to be solved by the third embodiment of the present invention >
In patent document 5, from the viewpoints of developability of a photosensitive resin composition, resolution of a resist pattern, adhesion, and flexibility, a combination of a binder polymer having a structural unit of (meth) acrylic acid, a structural unit of styrene or α -methylstyrene, and a structural unit of hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 1 to 12 carbon atoms, and a bisphenol type di (meth) acrylate monomer having 1 to 20 structural units of an ethyleneoxy group and 0 to 7 structural units of a propyleneoxy group has been studied with respect to a photosensitive resin composition.
Patent document 6 proposes that the content of the structural unit of styrene or a styrene derivative in the alkali-soluble polymer is 30 mass% or more and the weight average molecular weight of the addition polymerizable monomer is 1100 or more from the viewpoint of the space width and the porosity of the positive resist pattern.
Patent documents 5 and 6 each focus on a photosensitive resin composition containing a polymer having a structural unit of styrene and a specific monomer at a specific ratio, but the photosensitive resin compositions described in patent documents 5 and 6 have room for improvement from the viewpoint of achieving both the hole coverage of the resist pattern and the water remaining short-circuit failure suppression.
Accordingly, an object of the third embodiment of the present invention is to provide a photosensitive resin composition that can achieve both the hole coverage of a resist pattern and the suppression of a water-remaining short-circuit failure.
< problem to be solved by the fourth embodiment of the present invention >
In recent years, circuit boards are generally manufactured by a line in which substrates are sequentially processed while being conveyed in a fixed direction. In this case, the treatment of the substrate with the developer or the etchant is performed by spraying. In the formation of a resist pattern by photolithography, it is important that the resist line width after development does not vary. However, in the formation of a resist pattern by spray development, when the development time is short, the substrate surface of the developer is likely to be deviated, which may cause the above-mentioned problem, and therefore, the development time is required to be prolonged.
Here, the developing time is a time during which the substrate stays in the developing tank to be subjected to the developing process, and is, for example, a time determined to be 2 times the minimum developing time. The minimum development time is the minimum time required until the unexposed portion of the photosensitive resin layer is completely dissolved and removed, and varies depending on the concentration or temperature of the developer, the direction of the spray, the spray amount, the pressure, the frequency of vibration, and the like.
Here, it is considered that the dissolution reaction of the resist by the development is substantially controlled by the diffusion of the developer. Therefore, from the viewpoint of promoting development, it is necessary to actively supply the developing solution onto the substrate by spraying or the like. Since this supply takes some time, it is considered that, when the developing time is short, the supply of the developing solution is not sufficiently spread over the entire surface of the substrate, and the variation in the resist line width becomes significantly large. On the other hand, when the developing time is long, the supply of the developing solution on the substrate becomes uniform, and thus the variation in line width is considered to be small. Therefore, it is considered that the use of the photosensitive resin composition having a relatively slow minimum development time is effective from the viewpoint of suppressing variation in line width.
In patent document 5, from the viewpoints of developability of a photosensitive resin composition, resolution of a resist pattern, adhesion, and flexibility, a combination of a binder polymer having a structural unit of (meth) acrylic acid, a structural unit of styrene or α -methylstyrene, and a structural unit of hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 1 to 12 carbon atoms, and a bisphenol type di (meth) acrylate monomer having 1 to 20 structural units of an ethyleneoxy group and 0 to 7 structural units of a propyleneoxy group has been studied with respect to a photosensitive resin composition.
In patent document 6, from the viewpoint of the space width and the hole coverage of the positive resist pattern, it is proposed that the content of the structural unit of styrene or a styrene derivative in the alkali-soluble polymer is 30 mass% or more, and the weight average molecular weight of the addition polymerizable monomer is 1100 or more.
Patent documents 5 and 6 both focus on photosensitive resin compositions containing a polymer having a structural unit of styrene and a specific monomer at a specific ratio, but the photosensitive resin compositions described in patent documents 5 and 6 have room for improvement from the viewpoint of achieving both good resolution of a resist pattern and extension of a minimum development time.
Accordingly, a problem to be solved by the fourth embodiment of the present invention is to provide a photosensitive resin composition which can achieve both good resolution of a resist pattern and extension of a minimum development time.
Means for solving the problems
< means for solving the first problem >
The present inventors have found that the above object can be achieved by the following technical means, and have completed the first embodiment of the present invention. The first embodiment of the present invention is as follows.
[1]
A photosensitive resin composition comprising the following components (A) to (C),
(A) The components: alkali soluble polymer,
(B) The components: a compound having an olefinic double bond, and
(C) the components: photopolymerization initiator
A photosensitive resin layer formed from the photosensitive resin composition is laminated on a copper-clad laminate having a copper foil of 18 μm thickness, and the copper-clad laminate is irradiated with light in a pattern form having a line/space of 50 μm/30 μm and developed to form a cured resist pattern, and after copper etching treatment at 50 ℃ for 55 seconds, the bottom width of the copper wire pattern obtained by removing the cured resist pattern is 38 μm or more.
[2]
The photosensitive resin composition according to [1], wherein the component (A) is a copolymer having a content of a (meth) acrylic acid unit of 10 to 24 mass%.
[3]
The photosensitive resin composition according to [1] or [2], wherein the component (A) is a copolymer having a styrene unit content of 32% by mass or more and 60% by mass or less.
[4]
The photosensitive resin composition according to any one of [1] to [3], wherein the component (C) contains an acridine compound.
[5]
The photosensitive resin composition according to any one of [1] to [4], wherein the component (B) contains a pentaerythritol compound.
[6]
The photosensitive resin composition according to any one of [1] to [5], wherein the component (B) contains a trimethylolpropane compound.
[7]
The photosensitive resin composition according to any one of [1] to [6], wherein the component (B) contains a bisphenol A compound.
[8]
A photosensitive resin composition comprising the following components (A) to (C),
(A) the components: alkali soluble polymer,
(B) The components: a compound having an olefinic double bond, and
(C) the components: photopolymerization initiator
The component (A) comprises a copolymer having a content of (meth) acrylic acid units of 10 to 24 mass% and a content of styrene units of 32 mass% or more,
the component (C) contains an acridine compound.
[9]
The photosensitive resin composition according to [8], wherein the component (A) comprises a copolymer having a content of (meth) acrylic acid units of 10 to 24 mass% and a content of styrene units of 32 to 60 mass%.
[10]
The photosensitive resin composition according to [8] or [9], wherein the component (B) contains a pentaerythritol compound.
[11]
The photosensitive resin composition according to any one of [8] to [10], wherein the component (B) contains a trimethylolpropane compound.
[12]
The photosensitive resin composition according to any one of [8] to [11], wherein the component (B) contains a bisphenol A compound.
[13]
A photosensitive element obtained by laminating a photosensitive resin layer formed from the photosensitive resin composition according to any one of [1] to [12] on a support.
[14]
A method of forming a resist pattern, comprising:
a laminating step of laminating the photosensitive resin layer of the photosensitive element according to [13] on a conductor substrate,
An exposure step of exposing the laminated photosensitive resin composition layer, and
and a developing step of removing the unexposed portion with a developer.
[15]
The method of forming a resist pattern according to [14], wherein the laminating step is a step of laminating a photosensitive resin layer of the photosensitive element on the conductor substrate with a wetting agent interposed therebetween.
[16]
A method of manufacturing a circuit board, comprising:
a laminating step of laminating the photosensitive resin composition layer of the photosensitive element according to [13] on a conductor substrate,
An exposure step of exposing the laminated photosensitive resin composition layer,
A developing step of removing the unexposed portion with a developing solution,
A conductor pattern forming step of etching or plating the conductor substrate on which the resist pattern has been formed by the development, and
a peeling step of peeling off the resist pattern.
[17]
The method of manufacturing a circuit board according to item [16], wherein the laminating step is a step of laminating a photosensitive resin layer of the photosensitive element on the conductor substrate with a wetting agent interposed therebetween.
< means for solving the second problem >
The present inventors have found that the above object can be achieved by the following technical means, and have completed the second embodiment of the present invention. A second embodiment of the present invention is as follows.
[1]
A photosensitive resin composition comprising the following components (A) to (C),
(A) the components: an alkali-soluble polymer having an acid equivalent of 100 to 600,
(B) The components: a compound having an olefinic double bond, and
(C) the components: photopolymerization initiator
The component (A) contains a copolymer containing 50% by mass or more of styrene units,
the component (B) contains a compound represented by the following general formula (I),
Figure BDA0003379849860000111
{ wherein R is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n1, n2 and n3 are independently integers of 0 to 30, wherein the condition that n1+ n2+ n3 is 6 or more is satisfied. }
The content of the compound represented by the general formula (I) is 5% by mass or more relative to the solid content of the photosensitive resin composition, and the component (C) contains an acridine compound.
[2]
The photosensitive resin composition according to [1], wherein n1, n2 and n3 in the general formula (I) satisfy 20. gtoreq.n 1+ n2+ n3 > 9.
[3]
The photosensitive resin composition according to [1] or [2], wherein all R in the general formula (I) are hydrogen atoms.
[4]
The photosensitive resin composition according to any one of [1] to [3], wherein the component (B) further contains a pentaerythritol-modified monomer.
[5]
A photosensitive element obtained by laminating a photosensitive resin layer formed from the photosensitive resin composition according to any one of [1] to [4] on a support.
[6]
A method of forming a resist pattern, comprising:
a laminating step of laminating the photosensitive resin layer of the photosensitive element described in [5] on a conductor substrate, an exposure step of exposing the laminated photosensitive resin layer, and
and a developing step of removing the unexposed portion with a developer.
[7]
A method of manufacturing a circuit board, comprising:
a laminating step of laminating the photosensitive resin layer of the photosensitive element described in [5] on a conductor substrate, an exposure step of exposing the laminated photosensitive resin layer,
A developing step of removing the unexposed portion with a developing solution,
A conductor pattern forming step of etching or plating the conductor substrate on which the resist pattern has been formed by the development, and
a peeling step of peeling off the resist pattern.
< means for solving the third problem >
The present inventors have found that the above problems can be solved by the following technical means. A third embodiment of the present invention is as follows.
[1]
A photosensitive resin composition, comprising:
(A) an alkali-soluble polymer;
(B) a compound containing an ethylenically unsaturated bond; and
(C) a photopolymerization initiator;
the alkali-soluble polymer (A) contains 10 to 24 mass% of a structural unit of (meth) acrylic acid and 35 to 90 mass% of a structural unit of styrene based on the total mass of monomers constituting the alkali-soluble polymer (A),
the weight average molecular weight of the ethylenically unsaturated bond-containing compound (B) is 1200 or more.
[2]
The photosensitive resin composition according to [1], wherein the weight average molecular weight of the ethylenically unsaturated bond-containing compound (B) is 1300 or more.
[3]
The photosensitive resin composition according to [1] or [2], wherein 40% by mass or more of the ethylenically unsaturated bond-containing compound (B) is an alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the following general formula (II),
Figure BDA0003379849860000131
{ formula (II) wherein R3And R4Independently of one another, represents a hydrogen atom or a methyl group, A is C2H4B is C3H6，n1、n2、n3And n4To satisfy n1+n2+n3+n4The arrangement of the repeating units of- (a-O) -and- (B-O) -may be random or block, and in the case of a block, any one of- (a-O) -and- (B-O) -may be on the bisphenyl side }.
[4]
According to [3]The photosensitive resin composition, wherein n in the general formula (II)1、n2、n3And n4Satisfies n1+n2+n3+n4The relationship is 30 to 50.
[5]
According to [3]The photosensitive resin composition, wherein n in the general formula (II)1、n2、n3And n4Satisfies n1+n2+n3+n4The relationship is 2-10.
[6]
The photosensitive resin composition according to [1] or [2], wherein the ethylenically unsaturated bond-containing compound (B) comprises a tri (meth) acrylate compound represented by the following general formula (III),
Figure BDA0003379849860000141
{ formula (II) wherein R5、R6And R7Independently represents a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m2、m3And m4Independently of one another, m is an integer of 0 to 402+m3+m41 to 40, and m2+m3+m4In the case of 2 or more, X's are optionally the same as or different from each other }.
[7]
The photosensitive resin composition according to [1] or [2], wherein the ethylenically unsaturated bond-containing compound (B) comprises a urethane di (meth) acrylate compound represented by the following general formula (IV),
Figure BDA0003379849860000142
{ formula (II) wherein R8And R9Independently represents a hydrogen atom or a methyl group, Y represents an alkylene group having 2 to 6 carbon atoms, Z represents a divalent organic group, s and t are independently integers of 0 to 40, and s + t.gtoreq.1 }.
[8]
The photosensitive resin composition according to any one of [1] to [7], wherein the alkali-soluble polymer (A) further contains a structural unit of butyl (meth) acrylate.
[9]
The photosensitive resin composition according to any one of [1] to [8], which is used for direct image-wise exposure.
[10]
A method of forming a resist pattern, comprising:
a laminating step of laminating a photosensitive resin layer formed of the photosensitive resin composition according to any one of [1] to [9] on a support;
an exposure step of exposing the photosensitive resin layer; and
and a developing step of developing the exposed photosensitive resin layer.
[11]
A method of manufacturing a circuit board, comprising:
a laminating step of laminating a photosensitive resin layer formed of the photosensitive resin composition according to any one of [1] to [9] on a substrate;
an exposure step of exposing the photosensitive resin layer;
a developing step of developing the exposed photosensitive resin layer to obtain a substrate on which a resist pattern is formed;
A conductor pattern forming step of etching or plating the substrate on which the resist pattern is formed; and
a stripping step of stripping the resist pattern.
< means for solving the fourth problem >
The present inventors have found that the above object can be achieved by the following technical means, and have completed the fourth embodiment of the present invention. A fourth embodiment of the present invention is as follows.
[1]
A photosensitive resin composition comprising:
(A) an alkali-soluble polymer;
(B) a compound containing an ethylenically unsaturated bond; and
(C) a photopolymerization initiator;
the alkali-soluble polymer (A) comprises a first copolymer having a content of acid monomer units of less than 25 mass% and a content of aromatic monomer units of 30 mass% or more,
the weight average molecular weight of the ethylenically unsaturated bond-containing compound (B) is 900 or less.
[2]
The photosensitive resin composition according to [1], wherein the photopolymerization initiator (C) comprises an acridine compound.
[3]
The photosensitive resin composition according to [1] or [2], wherein the alkali-soluble polymer (A) comprises a second copolymer having a content ratio of an aromatic monomer unit of 45 to 90% by mass.
[4]
The photosensitive resin composition according to any one of [1] to [3], wherein the ethylenically unsaturated bond-containing compound (B) comprises a tri (meth) acrylate compound represented by the following general formula (III),
Figure BDA0003379849860000161
{ formula (II) wherein R5、R6And R7Independently represents a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m2、m3And m4Independently of one another, m is an integer of 0 to 402+m3+m40 to 40, and m2+m3+m4In the case of 2 or more, a plurality ofX are optionally the same or different from each other }.
[5]
The photosensitive resin composition according to any one of [1] to [4], wherein the ethylenically unsaturated bond-containing compound (B) comprises an alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the following general formula (II),
Figure BDA0003379849860000162
{ formula (II) wherein R3And R4Independently of one another, represents a hydrogen atom or a methyl group, A is C2H4B is C3H6，n1、n2、n3And n4To satisfy n1+n2+n3+n4The arrangement of the repeating units of- (a-O) -and- (B-O) -may be random or block, and in the case of a block, any one of- (a-O) -and- (B-O) -may be on the bisphenyl side }.
[6]
The photosensitive resin composition according to any one of [1] to [5], further comprising a compound represented by the following general formula (V) as the hindered phenol,
Figure BDA0003379849860000171
{ formula (II) wherein R51Represents an optionally substituted, straight-chain alkyl group, branched-chain alkyl group, aryl group, cyclohexyl group, straight-chain alkyl group sandwiching a divalent linking group, branched-chain alkyl group sandwiching a divalent linking group, cyclohexyl group sandwiching a divalent linking group, or aryl group sandwiching a divalent linking group, and R 52、R53And R54Each independently represents hydrogen, or an optionally substituted, straight-chain alkyl group, branched-chain alkyl group, aryl group, cyclohexyl group, straight-chain alkyl group sandwiching a divalent linking group, branched-chain alkyl group sandwiching a divalent linking group, cyclohexyl group sandwiching a divalent linking group, or aryl group sandwiching a divalent linking group. }.
[7]
The photosensitive resin composition according to any one of [1] to [6], which is used for direct image-wise exposure.
[8]
A photosensitive element obtained by laminating a photosensitive resin layer formed from the photosensitive resin composition according to any one of [1] to [7] on a support.
[9]
A method of forming a resist pattern, comprising:
a laminating step of laminating the photosensitive resin layer of the photosensitive element according to [8] on a conductor substrate;
an exposure step of exposing the laminated photosensitive resin layer; and
and a developing step of developing the exposed photosensitive resin layer.
[10]
A method of manufacturing a circuit board, comprising:
a laminating step of laminating the photosensitive resin layer of the photosensitive element according to [8] on a conductor substrate;
an exposure step of exposing the laminated photosensitive resin layer;
a developing step of developing the exposed photosensitive resin layer to form a resist pattern on the conductor substrate;
A conductor pattern forming step of etching or plating the conductor substrate on which the resist pattern is formed; and
a peeling step of peeling off the resist pattern.
ADVANTAGEOUS EFFECTS OF INVENTION
< Effect of the first embodiment >
According to the first embodiment of the present invention, there is provided a resist material in which a longitudinal/lateral difference in wiring width is suppressed when a fine conductor pattern is formed in a line.
< Effect of the second embodiment >
According to the second embodiment of the present invention, a novel photosensitive material is provided which has the performance normally required for photosensitive materials such as sensitivity and resolution at a high level and which is excellent in both development dispersibility and adhesion to fine patterns.
< Effect of the third embodiment >
According to the third embodiment of the present invention, a photosensitive resin composition capable of satisfying both the hole coverage of a resist pattern and the water remaining short-circuit failure suppression property is provided.
< Effect of the fourth embodiment >
According to the fourth embodiment of the present invention, there are provided a photosensitive resin composition capable of securing a good resolution of a resist pattern and extending a minimum development time, and a method for forming a resist pattern or a circuit board using the same.
Detailed Description
< first embodiment >
Hereinafter, a mode for carrying out the first embodiment of the present invention (hereinafter, simply referred to as "the present first embodiment") will be specifically described.
< photosensitive resin composition >
In the first embodiment, the photosensitive resin composition contains the following components (A) to (C),
(A) the components: alkali soluble polymer,
(B) The components: a compound having an olefinic double bond, and
(C) the components: a photopolymerization initiator.
[ (A) ingredient: alkali soluble polymer ]
The component (a) is not particularly limited as long as it is dissolved in a developer to be described later. Copolymers of (meth) acrylic acid with other monomers are preferred. The degree of dispersion of the copolymer, which is represented by the ratio of the weight average molecular weight (described later) to the number average molecular weight of the copolymer, is preferably 1 or more and 6 or less.
Examples of the (meth) acrylic acid include (meth) acrylic acid, pentenoic acid, unsaturated dicarboxylic anhydride, hydroxystyrene, and the like. Examples of the unsaturated dicarboxylic anhydride include maleic anhydride, itaconic anhydride, fumaric acid, and citraconic anhydride. Among them, (meth) acrylic acid is preferable.
The copolymerization ratio of the (meth) acrylic acid unit in the component (a) is preferably 10 to 24% by mass, more preferably 15 to 23% by mass, based on the total mass of all monomer units. When the content ratio of the (meth) acrylic acid unit is within this range, it is preferable from the viewpoint of suppressing the etching rate at the time of forming the conductor pattern (keeping the bottom width of the conductor line pattern at a constant or more) and suppressing the difference in the aspect ratio of the wiring width.
Examples of the other monomer include an unsaturated aromatic compound (which may be referred to as an "aromatic monomer"), an alkyl (meth) acrylate, an aralkyl (meth) acrylate, a conjugated diene compound, a polar monomer, and a crosslinkable monomer.
Examples of the unsaturated aromatic compound include styrene, α -methylstyrene, and vinylnaphthalene. Among them, styrene is preferable.
The alkyl (meth) acrylate is a concept including both a chain alkyl ester and a cyclic alkyl ester, and specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, n-tetradecyl (meth) acrylate, stearyl (meth) acrylate, and cyclohexyl (meth) acrylate.
Examples of the aralkyl (meth) acrylate include benzyl (meth) acrylate;
Examples of the conjugated diene compound include 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 2-phenyl-1, 3-butadiene, 1, 3-pentadiene, 2-methyl-1, 3-pentadiene, 1, 3-hexadiene, 4, 5-diethyl-1, 3-octadiene, and 3-butyl-1, 3-octadiene.
Examples of the polar monomer include:
hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and pentenol;
amino group-containing monomers such as 2-aminoethyl methacrylate;
amide group-containing monomers such as (meth) acrylamide and N-methylol (meth) acrylamide;
cyano group-containing monomers such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, and α -cyanoethylacrylate;
epoxy group-containing monomers such as glycidyl (meth) acrylate and 3, 4-epoxycyclohexyl (meth) acrylate;
and the like.
Examples of the crosslinkable monomer include trimethylolpropane triacrylate and divinylbenzene.
The component (a) is particularly preferably a copolymer of (meth) acrylic acid, styrene and other monomers.
The copolymerization ratio of the styrene unit in the component (a) is preferably 32% by mass or more, more preferably 35% by mass or more, based on the total mass of all monomer units. The copolymerization ratio of the styrene unit in the component (a) is preferably 60% by mass or less, more preferably 55% by mass or less, based on the total mass of all monomer units. When the copolymerization ratio of styrene, which has high hydrophobicity and is difficult to be compatible with the developer and the developing cleaning water, is set to the above range, it is preferable from the viewpoint of suppressing the difference in the aspect ratio of the wiring width.
The weight average molecular weight of the component (A) (when the component (A) includes a plurality of copolymers, the weight average molecular weight of the whole mixture) is preferably 5000 to 1000000, more preferably 10000 to 500000, and still more preferably 15000 to 100000. When the weight average molecular weight of the component (a) is adjusted to fall within this range, it is preferable from the viewpoint of adapting the development time at the time of resist pattern formation to the running state of the line used.
In the first embodiment, the content of the component (a) in the photosensitive resin composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 40 to 60% by mass based on the total solid content of the photosensitive resin composition (hereinafter, when not particularly described, the same applies to each component). The content is preferably 10 mass% or more from the viewpoint of maintaining alkali developability, and is preferably 90 mass% or less from the viewpoint of sufficiently exerting the performance as a resist of a resist pattern formed by exposure.
The copolymer having a content of the (meth) acrylic acid unit of 10 to 24% by mass and a content of the styrene unit of 32 to 60% by mass is preferably 8% by mass or more, more preferably 10% by mass or more, and particularly preferably 13.5/99.19 × 100% by mass or more, based on the total solid content of the photosensitive resin composition. The copolymer having a content of the (meth) acrylic acid unit of 10 to 24% by mass and a content of the styrene unit of 32 to 60% by mass may be 50% by mass or less, 40% by mass or less, 30% by mass or less, 27/99.19 × 100% by mass or less, or 20% by mass or less based on the total solid content of the photosensitive resin composition.
[ (B) ingredient: compounds having an olefinic double bond ]
(B) The component (B) may have 1 or more olefinic double bonds. Preference is given to using compounds having more than 2 olefinic double bonds.
As the compound (B) having 2 ethylenic double bonds, for example, bisphenol a compounds, particularly di (meth) acrylates of polyalkylene glycols obtained by adding 2 to 15 moles of alkylene oxides on average to each of both ends of bisphenol a, and the like are preferably used.
As the compound (B) having 3 olefinic double bonds, for example, trimethylolpropane compounds, particularly, tri (meth) acrylate esters of polyalkylene triols obtained by adding an average of 3 to 25 moles of alkylene oxides to trimethylolpropane, and the like are preferably used.
Further, as the compound (B) having 4 olefinic double bonds, for example, pentaerythritol compounds, particularly tetra (meth) acrylates of polyhydric alcohols obtained by adding an average of 4 to 35 moles of alkylene oxide to pentaerythritol, and the like are preferably used.
Examples of commercially available products of these include "BPE-500", "A-TMPT-3 EO", "A-9300-1 CL" (all manufactured by Nikkiso Kabushiki Kaisha):
"ARONIX M-327" (manufactured by Toyo Kagaku Co., Ltd.), and the like.
The content of the component (B) in the photosensitive resin composition of the first embodiment is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 50% by mass. The content is preferably 1 mass% or more from the viewpoint of suppressing curing failure and delay in development time, and is preferably 70 mass% or less from the viewpoint of suppressing cold flow and delay in peeling off of the cured resist.
As the component (B), a high molecular weight compound having a molecular weight of 1000 or more is preferably used. The molecular weight of the high molecular weight compound is more preferably 1300 or more and 3000 or less. The inclusion of such a high molecular weight compound is preferable from the viewpoint of suppressing the etching rate in forming a conductor pattern and suppressing the difference in the aspect ratio of the wiring width.
The proportion of the high-molecular weight compound in the component (B) is preferably 20% by mass or more, more preferably 20 to 50% by mass.
Here, the DD value is defined as an index of the double bond concentration of the component (B). The DD value is the number of double bonds of the monomers with respect to the weight average molecular weight, each monomer having a specific value.
When a monomer having a small DD value is used for the photosensitive resin composition, the film after photocuring tends to be easily flexible.
(B) When the components are composed of a plurality of kinds, the DD value of the composition is regarded as the weighted average of the DD value of each ethylenically unsaturated bond-containing compound and the compounding ratio.
From the viewpoint of suppressing the difference in the aspect ratio of the wiring width and improving the hole coverage, the DD value of the composition is preferably in the range of 0.10 to 0.13. More preferably 0.10 to 0.125.
[ (C) ingredient: photopolymerization initiator
(C) The component (B) is a component which generates a radical capable of initiating polymerization of the component (B) by irradiation with light.
Examples of the component (C) include aromatic ketone compounds, quinone compounds, benzoin ether compounds, benzoin compounds, benzil compounds, hexaarylbiimidazole compounds, and acridine compounds.
Among them, from the viewpoint of high resolution and good pore-capping property, an acridine compound is preferably used.
The content of the acridine compound in the photosensitive resin composition of the first embodiment is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, more preferably 0.2% by mass, more preferably 0.3% by mass, more preferably 0.4% by mass.
The content of the acridine compound in the photosensitive resin composition of the first embodiment is preferably 2.0% by mass or less, more preferably 1.8% by mass or less, more preferably 1.7% by mass or less, and more preferably 1.6% by mass or less. In the above range, a resist material capable of suppressing a difference in the width of the wiring between the longitudinal and lateral directions is preferably provided.
Examples of the acridine compound include acridine, 9-phenylacridine, 1, 6-bis (9-acridinyl) hexane, 1, 7-bis (9-acridinyl) heptane, 1, 8-bis (9-acridinyl) octane, 1, 9-bis (9-acridinyl) nonane, 1, 10-bis (9-acridinyl) decane, 1, 11-bis (9-acridinyl) undecane, 1, 12-bis (9-acridinyl) dodecane, and the like.
As the component (C), an acridine compound and a hexaarylbiimidazole compound are preferably used.
Examples of the hexaarylbiimidazole compound include 2- (o-chlorophenyl) -4, 5-diphenylimidazolyl dimer, 2 ', 5-tris- (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4', 5 '-diphenylimidazolyl dimer, 2, 4-bis- (o-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -diphenylimidazolyl dimer, 2,4, 5-tris- (o-chlorophenyl) -diphenylimidazolyl dimer, 2- (o-chlorophenyl) -bis-4, 5- (3, 4-dimethoxyphenyl) -imidazolyl dimer, 2' -bis- (2-fluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2, 3-difluoromethylphenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2, 4-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2, 5-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2, 6-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2,3, 4-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2,3, 5-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2,3, 6-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2,4, 5-trifluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 '-bis- (2,4, 6-trifluorophenyl) -4, 4', 5,5 '-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2' -bis- (2,3,4, 5-tetrafluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 '-bis- (2,3,4, 6-tetrafluorophenyl) -4, 4', 5,5 '-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2' -bis- (2,3,4,5, 6-pentafluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, and the like.
The content of the component (C) in the photosensitive resin composition of the first embodiment is preferably 0.1 to 2% by mass, more preferably 0.2 to 1.8% by mass, still more preferably 0.3 to 1.7% by mass, and particularly preferably 0.4 to 1.6% by mass. When the content of the component (C) is set in such a range, it is preferable from the viewpoint of obtaining good sensitivity and peeling characteristics.
The component (C) may further contain a sensitizer from the viewpoint of improvement of sensitivity and resolution. Examples of such sensitizers include N-aryl amino acids, organic halogen compounds, and other sensitizers.
Examples of the N-aryl amino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, and the like;
examples of the organic halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, dibromomethane, tribromomethylphenylsulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1, 1-trichloro-2, 2-bis (p-chlorophenyl) ethane, and chlorotriazine compounds.
Examples of the other sensitizers include: quinone compounds such as 2-ethylanthraquinone, octaethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-benzoanthraquinone, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2-methyl-1, 4-naphthoquinone, 2, 3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone;
aromatic ketone compounds such as benzophenone, michelson [4,4 '-bis (dimethylamino) benzophenone ], 4' -bis (diethylamino) benzophenone, and the like;
benzoin ether compounds such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin;
oxime ester compounds such as benzildimethylketal, benzildiethylketal, 1-phenyl-1, 2-propanedione-2-O-benzoyl oxime, and 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime;
and the like.
The content of the sensitizer in the first embodiment is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and still more preferably 0.1 to 2% by mass, from the viewpoints of the sensitivity of the composition and the releasability of the resist cured film.
In the photosensitive resin composition of the first embodiment, when an acridine compound and a n-aryl amino acid are used as the component (C) and they are used in combination within the above-described use ratio range, it is preferable from the viewpoint of suppressing the etching rate at the time of forming a conductor pattern and suppressing the difference in the aspect ratio of the wiring width.
[ other ingredients ]
The photosensitive resin composition of the first embodiment may contain other components in addition to the components (a) to (C) described above. Examples of such other components include leuco dyes, basic dyes, plasticizers, antioxidants, stabilizers, radical polymerization inhibitors, and solvents.
[ leuco dye ]
The leuco dye may be blended in the photosensitive resin composition of the first embodiment in order to impart appropriate color developability and excellent peeling characteristics to the resist cured film.
Specific examples of the leuco dye include leuco crystal violet (tris [4- (dimethylamino) phenyl ] methane), 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azabiphthalide, 1, 3-dimethyl-6-diethylaminofluorane, 2-chloro-3-methyl-6-dimethylaminofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, and mixtures thereof, 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-xylenylaminofluoran, 2- (2-chloroanilino) -6-dibutylaminofluoran, 3, 6-dimethoxyfluoran, 3, 6-di-N-butoxyfluoran, 1, 2-benzo-6-diethylaminofluoran, 1, 2-benzo-6-dibutylaminofluoran, 1, 2-benzo-6-ethylideneaminofluoran, 2-methyl-6- (N-p-toluene-N-ethylamino) fluoran, 2- (N-phenyl-N-methylamino) -6- (N-p-toluene-N-ethylamino) fluoran, 2- (3' -trifluoromethylanilino) -6-diethylaminofluoran, 3-chloro-6-cyclohexylaminofluoran, 2-methyl-6-cyclohexylaminofluoran, 3-methoxy-4-dodecyloxystyrenylquinoline, and the like. Among them, leuco crystal violet is preferable.
The content of the leuco dye in the photosensitive resin composition of the first embodiment is preferably 0.6 to 1.6% by mass, more preferably 0.7 to 1.2% by mass. By setting the use ratio of the leuco dye to this range, good color developability and good releasability can be achieved.
[ basic dye ]
Examples of the basic dye include basic green 1[ CAS number (the same applies below): 633-03-4] (e.g., Aizen Diamond Green GH, trade name, manufactured by Baotou chemical industries, Ltd.), Malachite Green oxalate [2437-29-8] (e.g., Aizen Malachite Green, trade name, manufactured by Baotou chemical industries, Ltd.), brilliant Green [633-03-4], fuchsin [632-99-5], methyl violet [603-47-4], methyl violet 2B [8004-87-3], crystal violet [548-62-9], methyl Green [82-94-0], Victoria Blue B [2580-56-5], basic Blue 7[2390-60-5] (e.g., Aizen Victoria Pure Blue BOH, trade name, manufactured by Baoto chemical industries, Ltd.), rhodamine B [81-88-9] (Hadamia, Rhodamine 6G [989-38-8], basic yellow 2[2465-27-2], Diamond Green (Diamond Green), and the like. Among them, 1 or more selected from basic green 1, malachite green oxalate, basic blue 7 and diamond green are preferable, and basic green 1 is particularly preferable from the viewpoint of hue stability and exposure contrast.
The content of the basic dye in the photosensitive resin composition of the first embodiment is preferably in the range of 0.001 to 3% by mass, more preferably in the range of 0.01 to 2% by mass, and still more preferably in the range of 0.01 to 1.2% by mass. By setting the use ratio in this range, both good color rendering properties and high sensitivity can be achieved.
[ solvent ]
The photosensitive resin composition of the first embodiment may be a mixture of the above-mentioned components (a) to (C) and optionally other components, or may be used in the form of a photosensitive resin composition preparation solution prepared by adding an appropriate solvent to these components.
Examples of the solvent used herein include:
ketone compounds such as Methyl Ethyl Ketone (MEK);
alcohols such as ethanol, ethanol and isopropanol;
and the like.
The solvent is preferably used in such a proportion that the viscosity of the photosensitive resin composition preparation liquid at 25 ℃ is 500 to 4000 mPasec.
< photosensitive element >
In the first embodiment, the photosensitive element is a laminate (photosensitive resin laminate) in which a photosensitive resin layer formed of the photosensitive resin composition is laminated on a support. If necessary, the photosensitive resin layer may have a protective layer on the surface thereof opposite to the support.
[ support ]
The support is preferably a transparent substrate that transmits light emitted from the exposure light source. Examples of such a support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, stretched films may also be used as needed.
The haze of the support is preferably 5 or less.
The support is advantageous in terms of image formability and economy when the thickness is small, but needs to maintain strength. In view of both, a support of 10 μm to 30 μm may be preferably used.
[ photosensitive resin composition layer ]
When the photosensitive resin composition used for forming the photosensitive resin composition layer contains a solvent, the solvent is preferably removed from the photosensitive resin composition layer, but the solvent remains.
The thickness of the photosensitive resin composition layer is preferably 5 to 100 μm, more preferably 7 to 60 μm. The thinner the thickness, the higher the resolution, and the thicker the thickness, the higher the film strength. Therefore, the thickness of the composition layer can be appropriately adjusted within the above range according to the use.
[ protective layer ]
The important characteristic of the protective layer is that the adhesion force with the photosensitive resin composition layer is sufficiently smaller than the adhesion force between the support and the photosensitive resin composition layer, and the protective layer can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film, or the like can be preferably used, and for example, a film excellent in peelability disclosed in jp 59-202457 a can be used.
The thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.
[ method for producing photosensitive element ]
The photosensitive element can be produced by sequentially laminating a support, a photosensitive resin layer, and a protective layer as needed. As a method for laminating the support, the photosensitive resin layer, and the protective layer, a known method can be used.
For example, a photosensitive resin composition is prepared as the photosensitive resin composition preparation liquid, and first, a support is coated with the photosensitive resin composition preparation liquid using a bar coater or a roll coater and dried, thereby forming a photosensitive resin composition layer formed of the photosensitive resin composition on the support. Next, a protective layer is laminated on the formed photosensitive resin composition layer as necessary, whereby a photosensitive element can be manufactured.
< method for forming resist Pattern >
A resist pattern can be formed on a substrate using the photosensitive element as described above.
The method for forming a resist pattern preferably includes the following steps in this order:
a laminating step of laminating the photosensitive resin layer of the photosensitive element on the conductor substrate,
An exposure step of exposing the laminated photosensitive resin composition layer, and
and a developing step of removing the unexposed portion with a developer.
The laminating step is preferably a step of laminating the photosensitive resin layer of the photosensitive element on the conductor substrate with the wetting agent interposed therebetween. As the wetting agent, 1 or more selected from pure water, deionized water and electrolyzed water, and a copper chelating agent (for example, 1 or more selected from the group consisting of an imidazole compound, a triazole compound, a pyridine compound and a pyrazole compound) are preferably contained.
In the method for forming a resist pattern according to the first embodiment, first, in the laminating step, a photosensitive resin composition layer is formed on a substrate using a laminator. Specifically, when the photosensitive element has a protective layer, the photosensitive resin composition layer is heated and pressure-bonded to the surface of the substrate using a laminator to laminate after the protective layer is peeled off.
As the substrate, a metal plate or an insulating substrate having a metal coating film is used. Examples of the material of the metal include copper, stainless steel (SUS), glass, and Indium Tin Oxide (ITO). These substrates may also have through holes for handling multilayer substrates.
Here, the photosensitive resin composition layer may be laminated only on one surface of the substrate surface, or may be laminated on both surfaces of the substrate as necessary. The heating temperature in this case is preferably 40 to 160 ℃. From the viewpoint of further improving the adhesion of the obtained resist pattern to the substrate, the thermocompression bonding is preferably performed 2 or more times. When the pressure bonding is performed 2 times or more, a two-stage laminator having two or more rollers may be used, or the pressure bonding may be performed by passing the laminate of the substrate and the photosensitive resin composition layer through the rollers several times.
Next, in the exposure step, the photosensitive resin composition layer is exposed by using an exposure machine. The exposure may be performed through the support without peeling the support, or may be performed after peeling the support as necessary.
By performing this exposure in a pattern, a resist film (resist pattern) having a desired pattern can be obtained after a developing step described later. The pattern-like exposure can be performed by either a method of exposing light through a photomask or a maskless exposure. When exposure is performed through a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time. The exposure amount may be measured using a light meter.
In the maskless exposure, exposure is performed on a substrate by a direct writing apparatus without using a photomask. As the light source, a semiconductor laser having a wavelength of 350nm to 410nm, an ultra-high pressure mercury lamp, or the like is used. In the maskless exposure, a drawing pattern is controlled by a computer, and the exposure amount is determined by the illuminance of an exposure light source and the moving speed of a substrate.
Next, in the developing step, the unexposed portions of the photosensitive resin composition layer are removed with a developing solution. After exposure, when the support is present on the photosensitive resin composition layer, it is preferably removed and then subjected to a developing step.
In the developing step, the unexposed portion is developed and removed using a developer composed of an aqueous alkali solution, thereby obtaining a resist image. As the aqueous alkali solution, for example, Na is preferably used2CO3、K2CO3And the like. The aqueous alkali solution is selected according to the characteristics of the photosensitive resin composition layer, and preferably 0.2 to 2 mass% of Na is used2CO3An aqueous solution. The aqueous alkali solution may contain a surfactant, a defoaming agent, a small amount of an organic solvent for promoting development, and the like.
The temperature of the developer in the developing step is preferably kept constant within a range of 20 ℃ to 40 ℃.
The resist pattern is obtained by the above-described steps. In some cases, the heating step may be further performed at 100 to 300 ℃. The heating step is preferably performed from the viewpoint of further improving the chemical resistance. The heating may be performed by a heating furnace using a suitable method such as hot air, infrared rays, or far infrared rays.
< method for forming circuit board >
The method for forming a circuit board according to the first embodiment preferably includes the following steps in this order:
a laminating step of laminating the photosensitive resin composition layer of the photosensitive element on the conductor substrate,
An exposure step of exposing the laminated photosensitive resin composition layer,
A developing step of removing the unexposed portion with a developing solution,
A conductor pattern forming step of etching or plating the conductor substrate on which the resist pattern has been formed by the development, and
a peeling step of peeling off the resist pattern.
The laminating step is preferably a step of laminating the photosensitive resin layer of the photosensitive element on the conductor substrate with the wetting agent interposed therebetween. As the wetting agent, 1 or more selected from pure water, deionized water and electrolyzed water, and a copper chelating agent (for example, 1 or more selected from the group consisting of an imidazole compound, a triazole compound, a pyridine compound and a pyrazole compound) are preferably contained.
In the conductor pattern forming step, a conductor pattern may be formed on the substrate having the resist pattern formed thereon by a known etching method or plating method with respect to the surface (e.g., copper surface) of the substrate exposed in the developing step.
In the stripping step, the substrate on which the conductor pattern is formed is brought into contact with an appropriate stripping liquid to strip and remove the resist pattern. Through this process, a desired circuit board is obtained.
The stripping liquid used in the stripping step is preferably an aqueous alkali solution. As the aqueous alkali solution, for example, a 2 to 5 mass% aqueous NaOH solution or an aqueous KOH solution is preferably used. A small amount of a water-soluble solvent such as alcohol may be added to the stripping solution. The temperature of the stripping solution in the stripping step is preferably 40 to 70 ℃.
In general, in the formation of a conductor pattern by etching, regardless of the etching rate, the etching time for achieving a desired wiring width can be adjusted by adjusting, for example, the transport rate of an etching line. However, if the etching rate is too high, the transport rate is too high, and there is a problem that the etching time cannot be practically set.
In recent years, circuit boards are generally manufactured by a line that sequentially processes substrates while conveying the substrates in a fixed direction, and there are cases where the lines of conductors are parallel (MD direction lines), perpendicular (TD direction lines), and skewed with respect to the conveying direction of the substrates. In particular, when the etching rate is high, the aspect ratio of the wiring width tends to become more significant.
As a result of intensive studies, the present inventors have found that a resist material in which a longitudinal/lateral difference in wiring width is suppressed when a fine conductor pattern is formed in a flow line can be provided when a photosensitive resin composition for forming a cured resist pattern has specific physical properties.
That is, the photosensitive resin composition of the first embodiment has the following features: a photosensitive resin layer formed from the photosensitive resin composition is laminated on a copper-clad laminate having a copper foil of 18 μm thickness, and the copper-clad laminate is irradiated with light in a pattern form having a line/space of 50 μm/30 μm and developed to form a cured resist pattern, and after copper etching treatment is performed at 50 ℃ for 55 seconds, the bottom width of the copper wire pattern obtained by removing the cured resist pattern is 38 μm or more (preferably 38 μm to 50 μm, and more preferably 40 μm to 45 μm).
The resist pattern undergoes swelling/shrinkage in each of the developing, washing and etching steps, and particularly the swelling/shrinkage in the washing step is large. It is considered that the swelling/shrinking of the resist pattern lowers the adhesion between the wiring and the resist pattern. It is considered that the resist pattern formed from the photosensitive resin composition of the first embodiment has small swelling/shrinkage in any of the developing, water washing and etching steps, and etching is difficult to proceed at the interface between the resist pattern and the wiring, and thus the longitudinal and lateral difference in the wiring width can be suppressed.
In the first embodiment, as a means for exhibiting the effect of the invention, a specific photosensitive resin composition is distinguished by focusing on the characteristics (the bottom width of the conductor line width is constant or more) when a specific analysis method (specific etching conditions) is used.
The adjustment of the width of the bottom of the conductor line width can be adjusted by appropriately setting the composition of the photosensitive resin composition.
In addition, the conductor pattern (wiring) formed by the method for forming a circuit board according to the first embodiment as described above can minimize the difference in the aspect ratio of the wiring width of the conductor pattern. The difference in the aspect ratio of the wiring width is represented by the difference TD-MD between the wiring width (TD) of the conductor line in the TD direction and the wiring width (MD) of the conductor line in the MD direction.
The absolute value of the difference in the vertical and horizontal widths of the wiring lines in the conductor pattern formed by the method for forming a conductor pattern according to the first embodiment is preferably 0 μm to 5 μm, and more preferably 0 μm to 3 μm.
The photosensitive resin composition, the photosensitive element, and the method for forming a circuit board according to the first embodiment can be suitably used for manufacturing, for example, a printed circuit board, a lead frame, a substrate having a concave-convex pattern, a semiconductor package, and the like.
The measurement methods of the various parameters described above are, unless otherwise specified, measured according to the measurement methods in the examples described below.
< second embodiment >
Hereinafter, a mode for carrying out the second embodiment of the present invention (hereinafter, simply referred to as "the present second embodiment") will be specifically described.
< photosensitive resin composition >
In the second embodiment, the photosensitive resin composition contains the following components (A) to (C),
(A) the components: an alkali-soluble polymer having an acid equivalent of 100 to 600,
(B) The components: a compound having an olefinic double bond, and
(C) the components: a photopolymerization initiator.
[ (A) ingredient: alkali soluble polymer ]
The component (A) has an acid equivalent of 100 to 600 (preferably 200 to 500, more preferably 250 to 450), and contains a copolymer containing 50 mass% or more of a styrene unit. Herein, in the present specification, a styrene unit means substituted or unsubstituted styrene. The substituent is not particularly limited, and examples thereof include an alkyl group, a halogen group, and a hydroxyl group.
(A) The component (B) is a copolymer of a styrene derivative and preferably an acid monomer or other monomer.
Examples of the acid monomer include (meth) acrylic acid, pentenoic acid, unsaturated dicarboxylic anhydride, and hydroxystyrene. Examples of the unsaturated dicarboxylic anhydride include maleic anhydride, itaconic anhydride, fumaric acid, and citraconic anhydride. Among them, (meth) acrylic acid is preferable.
Examples of the other monomer include an unsaturated aromatic compound (which may be referred to as an "aromatic monomer"), an alkyl (meth) acrylate, an aralkyl (meth) acrylate, a conjugated diene compound, a polar monomer, and a crosslinkable monomer.
Examples of the unsaturated aromatic compound include vinyl naphthalene.
The alkyl (meth) acrylate is a concept including both a chain alkyl ester and a cyclic alkyl ester, and specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, n-tetradecyl (meth) acrylate, stearyl (meth) acrylate, and cyclohexyl (meth) acrylate.
Examples of the aralkyl (meth) acrylate include benzyl (meth) acrylate;
examples of the conjugated diene compound include 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 2-phenyl-1, 3-butadiene, 1, 3-pentadiene, 2-methyl-1, 3-pentadiene, 1, 3-hexadiene, 4, 5-diethyl-1, 3-octadiene, and 3-butyl-1, 3-octadiene.
Examples of the polar monomer include:
hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and pentenol;
amino group-containing monomers such as 2-aminoethyl methacrylate;
amide group-containing monomers such as (meth) acrylamide and N-methylol (meth) acrylamide;
cyano group-containing monomers such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, and α -cyanoethylacrylate;
epoxy group-containing monomers such as glycidyl (meth) acrylate and 3, 4-epoxycyclohexyl (meth) acrylate;
and the like.
Examples of the crosslinkable monomer include trimethylolpropane triacrylate and divinylbenzene.
The component (A) is particularly preferably a copolymer of (meth) acrylic acid, styrene, and other monomers.
(A) Component (C) contains a copolymer 1 containing 50 mass% or more of styrene units. The amount of the styrene unit in the copolymer 1 is preferably 50 to 80% by mass, more preferably 51 to 70% by mass.
The component (a) in the second embodiment may be composed of the copolymer 1 alone, or may be a mixture of the copolymer 1 and another polymer. (A) The content of the copolymer 1 in the component (a) is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 20 to 70% by mass.
The other polymer is preferably a copolymer of the above-described acid monomer and another monomer, which is not the copolymer 1 (copolymer 2).
(A) The weight average molecular weight of component (A) (when component (A) contains a plurality of copolymers, the weight average molecular weight of the whole mixture) is preferably 5000 to 1000000, more preferably 10000 to 500000, and still more preferably 15000 to 100000. When the weight average molecular weight of the component (a) is adjusted within this range, it is preferable from the viewpoint of adapting the development time at the time of resist pattern formation to the running state of the line used. The degree of dispersion of the copolymer represented by the ratio of the weight average molecular weight to the number average molecular weight of the component (a) is preferably 1 or more and 6 or less.
In the second embodiment, the content of the component (a) in the photosensitive resin composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 40 to 60% by mass based on the total solid content of the photosensitive resin composition (hereinafter, unless otherwise specified, the same applies to the respective components). The content is preferably 10 mass% or more from the viewpoint of maintaining alkali developability, and is preferably 90 mass% or less from the viewpoint of sufficiently exerting the performance as a resist of a resist pattern formed by exposure.
[ (B) ingredient: compounds having an olefinic double bond ]
(B) The component (C) is not particularly limited as long as it has 1 or more olefinic double bonds. The component (B) in the second embodiment contains a compound represented by the following general formula (I) as an essential compound (B1).
Figure BDA0003379849860000351
{ wherein R is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n1, n2 and n3 are independently integers of 0 to 30, wherein the condition that n1+ n2+ n3 is 6 or more is satisfied. }
In the formula (I), R is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. n1, n2 and n3 are each independently an integer of preferably 1 to 30, more preferably 3 to 21.
In the formula (I), from the viewpoint of improving development dispersibility, the value of n1+ n2+ n3 is preferably more than 9 and 20 or less, more preferably 15 or more and 20 or less.
In the formula (I), from the viewpoint of improving development dispersibility, at least 1R is preferably a hydrogen atom, and more preferably all R are hydrogen atoms.
Further, in the formula (I), from the viewpoint of satisfying both development dispersibility and adhesion, it is particularly preferable that all R are hydrogen atoms, and the value of n1+ n2+ n3 is 15 or more and 20 or less.
The compound represented by formula (I) is synthesized by a known method, and for example, can be obtained by adding 3 moles of (meth) acrylic acid to an adduct obtained by adding 6 equivalents or more of ethylene oxide to trimethylolpropane, or by performing transesterification.
Preferable specific examples of the compound represented by the formula (I) include Ethylene Oxide (EO) -modified trimethylolpropane tri (meth) acrylate (EO addition molar total number is 6 to 20).
The component (B) in the second embodiment may be composed of the compound (B1) alone, or may be a mixture of the compound (B1) and another component (B).
When the component (B) in the second embodiment is a mixture, the content of the compound (B1) in the mixture is preferably 10% by mass or more, more preferably 10% by mass to 50% by mass, and still more preferably 15% by mass to 35% by mass, based on the total mass of the mixture.
The content of the compound (B1) in the photosensitive resin composition of the second embodiment is preferably 5% by mass or more, more preferably 5.5% by mass to 30% by mass, and still more preferably 6% by mass to 20% by mass, based on the total solid content of the photosensitive resin composition.
Here, although the mechanism of realizing a photosensitive resin composition having excellent development dispersibility and excellent adhesion to a fine pattern by including an alkali-soluble polymer having a specific acid equivalent and a specific amount of a styrene unit, the (B1) component, and acridine is not determined, it is presumed that the interaction between the styrene unit and the acridine component (due to pi electron stacking) and the interaction between the acid monomer and the (B1) component (due to hydrogen bonding) are well represented and the overall compatibility is improved, which is advantageous for the above characteristics.
In the second embodiment, the component (B) preferably contains a pentaerythritol-modified monomer (hereinafter referred to as "compound (B2)") together with the compound (B1) from the viewpoint of development dispersibility. As the compound (B2), a tetra (meth) acrylate of a polyol obtained by adding an alkylene oxide to pentaerythritol in an amount of preferably 4 to 35 moles, more preferably 8 to 28 moles, and still more preferably 12 to 20 moles on average is used.
(B) The content of the compound (B2) in the component (a) is preferably 10 to 40 mass%, more preferably 15 to 30 mass%, based on the total mass of the component (B).
The content of the compound (B2) in the photosensitive resin composition of the second embodiment is preferably 1% by mass or more, more preferably 1% by mass to 20% by mass, and still more preferably 5% by mass to 15% by mass.
(B) Ingredient (a) may also contain a compound having an olefinic double bond other than the compounds (B1) and (B2).
(B) The ingredients may also include the following:
bisphenol a compounds such as di (meth) acrylates of polyalkylene glycols obtained by adding an average of 2 to 15 moles of alkylene oxide to each end of bisphenol a;
a compound having 3 olefinic double bonds (excluding B1), for example, a tri (meth) acrylate of a polyalkylene triol obtained by adding an alkylene oxide to trimethylolpropane in an amount of 3 to 25 moles on average.
The content of the component (B) in the photosensitive resin composition of the second embodiment is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 50% by mass. The content thereof is preferably 1 mass% or more from the viewpoint of suppressing the curing failure and the development time lag, and is preferably 70 mass% or less from the viewpoint of suppressing the generation of aggregates in the developer.
[ (C) ingredient: photopolymerization initiator
(C) The component (B) is a component which generates a radical capable of initiating polymerization of the component (B) by irradiation with light.
In the second embodiment, an acridine compound can be used as the photopolymerization initiator (B). Further, the acridine compound may be used in combination with other photopolymerization initiators. The acridine compound is preferably used to improve the sensitivity and resolution of the photosensitive resin composition of the second embodiment.
Examples of the acridine compound include 1, 7-bis (9, 9' -acridinyl) heptane, 9-phenylacridine, 9-methylacridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9-ethoxyacridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- (4-tert-butylphenyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-chlorophenyl) acridine, 9-phenylacridine, and the like, 9- (4-bromophenyl) acridine, 9- (3-methylphenyl) acridine, 9- (3-tert-butylphenyl) acridine, 9- (3-acetylphenyl) acridine, 9- (3-dimethylaminophenyl) acridine, 9- (3-diethylaminophenyl) acridine, 9- (3-chlorophenyl) acridine, 9- (3-bromophenyl) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, 9- (4-pyridyl) acridine and the like.
Examples of other photopolymerization initiators include:
2- (o-chlorophenyl) -4, 5-diphenylimidazolyl dimer, 2 ', 5-tris- (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4 ', 5 ' -diphenylimidazolyl dimer, 2, 4-bis- (o-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -diphenylimidazolyl dimer, 2,4, 5-tris- (o-chlorophenyl) -diphenylimidazolyl dimer, 2- (o-chlorophenyl) -bis-4, 5- (3, 4-dimethoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2-fluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, p-chlorophenyl-4, 5 ' -diphenylimidazolyl dimer, p-chlorophenyl-tolylimidazolyl dimer, p-tolylsulfonyl dimer, p-tolylp-tolylo-imidazolyl dimer, p-tolylp-imidazole dimer, p-tolylp-dimer, 2, p-4, p-tolylp-4, p-y-tolylp-4, p-tolylp-y-tolylp-y dimer, p-4, p-tolylp-y-tolylp-y-tolylp-imidazole dimer, p-tolylp-phenylene-tolylp-y-phenylene-y-p-y-phenylene-p-phenylene-p-y-tolylp-y-phenylene-2, p-phenylene-y-2, p-y-2, p-phenylene-2, p-4, p-2, p-bis (p-2, p-y-2, p-bis-4, p-4, 2,2 ' -bis- (2, 3-difluoromethylphenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2, 4-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2, 5-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2, 6-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2,3, 4-trifluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 '-bis- (2,3, 5-trifluorophenyl) -4, 4', 5,5 '-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2' -bis- (2,3, 6-trifluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 '-bis- (2,4, 5-trifluorophenyl) -4, 4', 5,5 '-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2' -bis- (2,4, 6-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2,3,4, 5-tetrafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, hexaarylbiimidazole compounds such as 2,2 '-bis- (2,3,4, 6-tetrafluorophenyl) -4, 4', 5,5 '-tetrakis- (3-methoxyphenyl) -imidazolyl dimer and 2, 2' -bis- (2,3,4,5, 6-pentafluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer;
2,4, 5-triarylimidazole dimers such as 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-bis (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, and 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer (excluding substances belonging to the hexaarylbiimidazole compound);
aromatic ketones such as benzophenone, N ' -tetramethyl-4, 4 ' -dimethylaminobenzophenone (michelson), N ' -tetraethyl-4, 4 ' -diaminobenzophenone, 4-methoxy-4 ' -dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropanone-1;
quinone compounds such as 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-benzoanthraquinone, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2-methyl-1, 4-naphthoquinone, and 2, 3-dimethylanthraquinone;
benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether;
benzil derivatives such as benzil methyl ketal;
N-phenylglycine derivatives, coumarin-based compounds, 4' -bis (diethylamino) benzophenone, and the like.
The content of the acridine compound in the photosensitive resin composition of the second embodiment is preferably in the range of 0.001 to 2 mass%, more preferably 0.01 to 1.5 mass%, and still more preferably 0.1 to 1 mass%.
The content of the component (C) (the content of the entire component (C) including the acridine compound) in the photosensitive resin composition of the second embodiment is preferably 0.1 to 2 mass%, more preferably 0.2 to 1.8 mass%, still more preferably 0.3 to 1.7 mass%, and particularly preferably 0.4 to 1.6 mass%.
From the viewpoint of improving sensitivity and resolution, the component (C) may further contain a sensitizer. Examples of such sensitizers include N-aryl amino acids, organic halogen compounds, and other sensitizers.
Examples of the N-aryl amino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, and the like;
examples of the organic halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, dibromomethane, tribromomethylphenylsulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1, 1-trichloro-2, 2-bis (p-chlorophenyl) ethane, and chlorotriazine compounds.
Examples of the other sensitizers include:
quinone compounds such as 2-ethylanthraquinone, octaethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-benzoanthraquinone, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2-methyl-1, 4-naphthoquinone, 2, 3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone;
aromatic ketone compounds such as benzophenone, michelson [4,4 '-bis (dimethylamino) benzophenone ], 4' -bis (diethylamino) benzophenone, and the like;
benzoin ether compounds such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin;
oxime ester compounds such as benzildimethylketal, benzildiethylketal, 1-phenyl-1, 2-propanedione-2-O-benzoyl oxime, and 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime;
and the like.
The content of the sensitizer in the photosensitive resin composition of the second embodiment is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and still more preferably 0.1 to 2% by mass, from the viewpoints of the sensitivity of the composition and the releasability of the resist cured film.
[ other ingredients ]
The photosensitive resin composition of the second embodiment may contain other components in addition to the components (a) to (C) described above. Examples of the other components include coloring substances, halogen compounds, stabilizers, and solvents.
As the coloring matter, respectively, leuco dyes and other coloring matters;
examples of the stabilizer include a radical polymerization inhibitor, a benzotriazole compound, and a carboxybenzotriazole compound.
< leuco dyes >
Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [ leuco crystal violet ], bis (4-dimethylaminophenyl) phenylmethane [ leuco malachite green ], and the like. Especially, leuco crystal violet is preferably used from the viewpoint of good contrast.
The content of the leuco dye in the photosensitive resin composition is preferably 0.1 to 10% by mass. When the content of the leuco dye is adjusted to 0.1% by mass or more, it is preferable from the viewpoint of obtaining the contrast between the exposed portion and the unexposed portion, and on the other hand, when the content is adjusted to 10% by mass or less, it is preferable from the viewpoint of maintaining the storage stability.
< other coloring matter >
Examples of the other coloring materials include magenta, phthalocyanine GREEN, basic bright yellow (Auramine Base), paramagenta (paragenta), crystal violet, methyl orange, nile blue 2B, victoria blue, malachite GREEN (Aizen (registered trademark) MALACHITE GREEN, manufactured by shinguo chemical corporation), basic blue 20, and DIAMOND GREEN (Aizen (registered trademark) DIAMOND GREEN GH, manufactured by shinguo chemical corporation).
The content of the other coloring matter in the photosensitive resin composition is preferably 0.001 to 1% by mass. When the content is adjusted to 0.001 mass% or more, it is preferable from the viewpoint of improving handling properties, while when the content is adjusted to 1 mass% or less, it is preferable from the viewpoint of maintaining storage stability.
< halogen Compound >
From the viewpoint of adhesiveness and contrast, it is a preferable embodiment to use a leuco dye and the following halogen compound in combination in the photosensitive resin composition.
Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1, 1-trichloro-2, 2-bis (p-chlorophenyl) ethane, and chlorotriazine compounds. Tribromomethyl phenyl sulfone is particularly preferred. When the content of the halogen compound in the photosensitive resin composition is 0.01 to 3% by mass, it is preferable from the viewpoint of maintaining the storage stability of the hue of the photosensitive layer.
< inhibitor of radical polymerization, benzotriazole compound, and carboxybenzotriazole compound >
Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, 2, 6-di-t-butyl-p-cresol, 2 '-methylenebis (4-methyl-6-t-butylphenol), 2' -methylenebis (4-ethyl-6-t-butylphenol), nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosamine.
Examples of the benzotriazole compound include 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole and the like.
Examples of the carboxybenzotriazole compound include 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole and the like.
The total content of the radical polymerization inhibitor, the benzotriazole compound, and the carboxybenzotriazole compound in the photosensitive resin composition is preferably 0.01 to 3% by mass, and more preferably 0.05 to 1% by mass. When the content is adjusted to 0.01% by mass or more, it is preferable from the viewpoint of imparting storage stability to the photosensitive resin composition, and on the other hand, when the content is adjusted to 3% by mass or less, it is preferable from the viewpoint of maintaining sensitivity and suppressing discoloration of the dye.
< plasticizer >
The photosensitive resin composition may contain a plasticizer as necessary. Examples of the plasticizer include phthalic acid esters such as diethyl phthalate, o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, acetyl tri-n-propyl citrate, acetyl tri-n-butyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether.
The content of the plasticizer in the photosensitive resin composition is preferably 1 to 50% by mass, and more preferably 1 to 30% by mass. When the content is adjusted to 1 mass% or more, it is preferable from the viewpoint of suppressing the delay of the development time and providing flexibility to the cured film, while when the content is adjusted to 50 mass% or less, it is preferable from the viewpoint of suppressing the insufficient curing and the edge fusion.
< solvent >
The photosensitive resin composition may also contain a solvent. Examples of the solvent include ketones typified by Methyl Ethyl Ketone (MEK); alcohols typified by methanol, ethanol, and isopropanol, and the like. The solvent is preferably added to the photosensitive resin composition so that the viscosity of a solution of the photosensitive resin composition applied to the support film is 500 to 4000 mPas at 25 ℃.
< photosensitive element >
In the second embodiment, the photosensitive element is a laminate (photosensitive resin laminate) obtained by laminating a photosensitive resin layer formed of the photosensitive resin composition on a support. The photosensitive element may have a protective layer on the surface of the photosensitive resin layer opposite to the support, if necessary.
[ support ]
The support is preferably a transparent substrate that transmits light emitted from the exposure light source. Examples of the support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, stretched films may also be used as needed.
The haze of the support is preferably 5 or less.
The support is advantageous in terms of image formability and economy when the thickness is small, but needs to maintain strength. In view of both, a support of 10 μm to 30 μm may be preferably used.
[ photosensitive resin layer ]
When the photosensitive resin composition used for forming the photosensitive resin layer contains a solvent, the solvent is preferably removed from the photosensitive resin layer, but may remain in the photosensitive resin layer.
The thickness of the photosensitive resin layer is preferably 5 to 100 μm, more preferably 7 to 60 μm. The thinner the thickness, the higher the resolution, and the thicker the thickness, the higher the film strength. Therefore, the thickness of the photosensitive resin layer can be appropriately selected in the range of 5 μm to 100 μm depending on the application.
[ protective layer ]
The important characteristic of the protective layer is that the adhesion force with the photosensitive resin layer is sufficiently smaller than the adhesion force between the support and the photosensitive resin layer, and the protective layer can be easily peeled off. As the protective layer, not only a polyethylene film, a polypropylene film, or the like, but also a film excellent in releasability as disclosed in, for example, Japanese patent application laid-open No. 59-202457 can be preferably used.
The thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.
[ method for producing photosensitive element ]
The photosensitive element can be produced by sequentially laminating a support, a photosensitive resin layer, and a protective layer as needed. As a method for laminating the support, the photosensitive resin layer, and the protective layer, a known method can be used.
For example, a solvent is added to and mixed with a photosensitive resin composition to prepare a prepared liquid, and the prepared liquid is further coated on a support using a bar coater or a roll coater and dried to form a photosensitive resin layer formed of the photosensitive resin composition on the support. Next, a protective layer is laminated on the formed photosensitive resin layer as necessary, whereby a photosensitive element can be manufactured.
< method for forming resist Pattern >
A resist pattern can be formed on a substrate using the photosensitive element as described above.
The method for forming a resist pattern preferably includes the following steps in this order:
a laminating step of laminating the photosensitive resin layer of the photosensitive element on the conductor substrate,
An exposure step of exposing the laminated photosensitive resin layer, and
and a developing step of removing the unexposed portion with a developer.
The laminating step is preferably a step of laminating the photosensitive resin layer of the photosensitive element on the conductor substrate with the wetting agent interposed therebetween. As the wetting agent, 1 or more selected from pure water, deionized water and electrolyzed water, and a copper chelating agent (for example, 1 or more selected from the group consisting of an imidazole compound, a triazole compound, a pyridine compound and a pyrazole compound) are preferably contained.
In the method for forming a resist pattern according to the second embodiment, first, in the laminating step, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive element has a protective layer, the photosensitive resin layer is heated and pressed against the surface of the substrate using a laminator after the protective layer is peeled off, and the photosensitive element is laminated.
As the substrate, a metal plate or an insulating substrate having a metal coating film is used. Examples of the material of the metal include copper, stainless steel (SUS), glass, and Indium Tin Oxide (ITO). These substrates may also have through holes for handling multilayer substrates.
The photosensitive resin layer may be laminated on only one surface of the substrate surface, or may be laminated on both surfaces of the substrate as necessary. The heating temperature at the time of lamination is preferably 40 to 160 ℃. From the viewpoint of further improving the adhesion of the obtained resist pattern to the substrate, the thermocompression bonding is preferably performed 2 or more times. When the pressure bonding is performed 2 times or more, a two-stage laminator having two or more rollers may be used, or the pressure bonding may be performed by passing the laminate of the substrate and the photosensitive resin layer through the rollers several times.
Next, in the exposure step, the photosensitive resin layer is exposed by using an exposure machine. The exposure may be performed through the support without peeling the support, or may be performed after peeling the support as necessary.
By performing this exposure in a pattern, a resist film (resist pattern) having a desired pattern can be obtained after a developing step described later. The pattern-like exposure can be performed by either a method of exposing light through a photomask or a maskless exposure. When exposure is performed through a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time. The exposure amount may be measured using a light meter.
In the maskless exposure, exposure is performed on a substrate by a direct writing apparatus without using a photomask. As the light source, a semiconductor laser having a wavelength of 350nm to 410nm, an ultra-high pressure mercury lamp, or the like is used. In the maskless exposure, a drawing pattern is controlled by a computer, and the exposure amount is determined by the illuminance of an exposure light source and the moving speed of a substrate.
Next, in the developing step, the unexposed portions of the photosensitive resin layer are removed with a developer. When the support is provided on the photosensitive resin layer after exposure, it is preferably removed and subjected to a developing step.
In the developing step, the unexposed portion is developed and removed using a developer composed of an aqueous alkali solution, thereby obtaining a resist image. As the aqueous alkali solution, for example, Na is preferably used2CO3、K2CO3And the like. The alkali aqueous solution is selected according to the characteristics of the photosensitive resin layer, and preferably 0.2 to 2 mass% of Na is used 2CO3An aqueous solution. The aqueous alkali solution may contain a surfactant, a defoaming agent, a small amount of an organic solvent for promoting development, and the like.
The temperature of the developer in the developing step is preferably kept constant within a range of 20 ℃ to 40 ℃.
The resist pattern is obtained by the above-described steps. In some cases, the heating step may be further performed at 100 to 300 ℃. The heating step is preferably performed from the viewpoint of further improving the chemical resistance. The heating may be performed by a heating furnace using a suitable method such as hot air, infrared rays, or far infrared rays.
< method for forming circuit board >
The method for forming a circuit board according to the second embodiment preferably includes the following steps in this order:
a laminating step of laminating the photosensitive resin layer of the photosensitive element on the conductor substrate,
An exposure step of exposing the laminated photosensitive resin layer,
A developing step of removing the unexposed portion with a developing solution,
A conductor pattern forming step of etching or plating the conductor substrate on which the resist pattern has been formed by the development, and
a peeling step of peeling off the resist pattern.
The laminating step is preferably a step of laminating the photosensitive resin layer of the photosensitive element on the conductor substrate with the wetting agent interposed therebetween. As the wetting agent, 1 or more selected from pure water, deionized water and electrolyzed water, and a copper chelating agent (for example, 1 or more selected from the group consisting of an imidazole compound, a triazole compound, a pyridine compound and a pyrazole compound) are preferably contained.
In the conductor pattern forming step, a conductor pattern may be formed on the substrate having the resist pattern formed thereon by a known etching method or plating method with respect to the surface (e.g., copper surface) of the substrate exposed in the developing step.
In the stripping step, the substrate on which the conductor pattern is formed is brought into contact with an appropriate stripping liquid to strip and remove the resist pattern. Through this process, a desired circuit board is obtained.
The stripping liquid used in the stripping step is preferably an aqueous alkali solution. As the aqueous alkali solution, for example, a 2 to 5 mass% aqueous NaOH solution or an aqueous KOH solution is preferably used. A small amount of a water-soluble solvent such as alcohol may be added to the stripping solution. The temperature of the stripping solution in the stripping step is preferably 40 to 70 ℃.
The photosensitive resin composition, the photosensitive element, and the method for forming a circuit board according to the second embodiment can be suitably used for manufacturing, for example, a printed circuit board, a lead frame, a substrate having a concave-convex pattern, a semiconductor package, and the like.
The measurement methods of the various parameters described above are, unless otherwise specified, measured according to the measurement methods in the examples described below.
< third embodiment >
Hereinafter, a mode for carrying out the third embodiment of the present invention (hereinafter, also simply referred to as "the present third embodiment") will be specifically described.
< photosensitive resin composition >
In the third embodiment, the photosensitive resin composition comprises (a) an alkali-soluble polymer, (B) an ethylenically unsaturated bond-containing compound, and (C) a photopolymerization initiator. The photosensitive resin composition may further contain other components such as (D) additives, as desired.
In the present specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid, "(meth) acryloyl group" means acryloyl group or methacryloyl group, and "(meth) acrylate" means "acrylate" or "methacrylate".
(A) Alkali soluble polymer
(A) The alkali-soluble polymer is a polymer soluble in an alkali substance. In the third embodiment, from the viewpoint of satisfying both the pinhole characteristic of the resist pattern and the water remaining short-circuit failure suppressing characteristic, it is preferable that the (a) alkali-soluble polymer contains 10 to 24 mass% of a structural unit of (meth) acrylic acid and 35 to 90 mass% of a structural unit of styrene based on the total mass of the monomers constituting the (a) alkali-soluble polymer.
The content of the (meth) acrylic acid structural unit in the (a) alkali-soluble polymer is preferably 24 mass% or less from the viewpoint of suppressing a water residual short circuit failure, and is preferably 10 mass% or more from the viewpoint of ensuring alkali developability and alkali releasability, based on the total mass of the monomers constituting the (a) alkali-soluble polymer. The upper limit of the content is more preferably 23 mass% or 22.5 mass%, and the lower limit is more preferably 11 mass%, 15 mass%, 18 mass% or 20 mass%. The water residual short-circuit failure is strongly correlated with the hydrophobicity of the cured resist, and the water residual short-circuit failure can be suppressed by increasing the water contact angle, which is the hydrophobicity of the resist.
Regarding the content of the (meth) acrylic structural unit in the (a) alkali-soluble polymer, the acid equivalent of the (a) alkali-soluble polymer (in the case where the (a) component includes a plurality of copolymers, the acid equivalent is relative to the whole mixture) is preferably 100 or more from the viewpoint of the development resistance of the photosensitive resin layer, the development resistance, the resolution, and the adhesion of the resist pattern, and is preferably 900 or less from the viewpoint of the development resistance and the peeling property of the photosensitive resin layer. (A) The alkali-soluble polymer preferably has an acid equivalent of 250 to 600, more preferably 350 to 500. The acid equivalent means the mass of the linear polymer having 1 equivalent of carboxyl group therein.
The content of the styrene structural unit in the (a) alkali-soluble polymer is preferably 90 mass% or less from the viewpoint of developability, and is preferably 35 mass% or more from the viewpoint of resolution and water remaining short-circuit failure suppression, based on the total mass of the monomers constituting the (a) alkali-soluble polymer. The upper limit of the content is more preferably 85 mass%, 80 mass%, 70 mass%, or 60 mass% from the viewpoint of developability and prevention of a delay in peeling time, and the lower limit is more preferably 36 mass%, 38 mass%, 40 mass%, or 42 mass% from the viewpoint of resolution and suppression of a water remaining short circuit failure.
From the viewpoint of improving the hole coverage of the resist pattern, it is preferable that the (a) alkali-soluble polymer further contains a structural unit of butyl (meth) acrylate. The structural unit of butyl (meth) acrylate may also include a repeating unit derived from at least 1 selected from the group consisting of n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate.
From the viewpoint of satisfying both the pore capping property and the water remaining short-circuit failure suppressing property, the content of the structural unit of butyl (meth) acrylate in the alkali-soluble polymer (a) is preferably within a range of 0.1 to 5% by mass, more preferably 0.3 to 1% by mass, based on the total mass of the monomers constituting the alkali-soluble polymer (a).
(A) The alkali-soluble polymer may be a single copolymer, or a mixture of a plurality of copolymers and/or a mixture of a plurality of homopolymers, as long as it contains 10 to 24 mass% of a structural unit of (meth) acrylic acid and 35 to 90 mass% of a structural unit of styrene based on the total mass of the monomers constituting the alkali-soluble polymer (a).
(A) The alkali-soluble polymer may include poly (meth) acrylic acid, poly (butyl (meth) acrylate), polystyrene, a copolymer obtained by copolymerizing a copolymerization component including 1 or more kinds of (meth) acrylic acid and/or styrene and the first monomer described later and/or 1 or more kinds of the second monomer described later, and the like.
The first monomer is a monomer having a carboxyl group in the molecule (excluding (meth) acrylic acid). Examples of the first monomer include fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester.
The second monomer is a monomer (excluding styrene) which is non-acidic and has at least 1 polymerizable unsaturated group in the molecule. Examples of the second monomer include vinyl alcohol esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, and vinyl acetate; (meth) acrylonitrile; polymerizable styrene derivatives, and the like.
Among them, from the viewpoint of improving the coverage of the resist pattern, n-butyl (meth) acrylate, isobutyl (meth) acrylate, or tert-butyl (meth) acrylate is preferable, and from the viewpoint of coverage, n-butyl (meth) acrylate is more preferable, and from the viewpoint of improving the resolution and the water remaining short-circuit failure suppressing property, a polymerizable styrene derivative is preferable.
Examples of the polymerizable styrene derivative include methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer.
The alkali-soluble polymer is preferably synthesized as follows: the synthesis is carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by mixing the above monomers and diluting the mixture with a solvent such as acetone, methyl ethyl ketone, methanol, ethanol, n-propanol, or isopropyl alcohol, and heating and stirring the mixture. The synthesis may be performed while a part of the mixture is added dropwise to the reaction solution. After the completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. As a synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
(A) The weight average molecular weight of the alkali-soluble polymer (when component (a) includes a plurality of copolymers, the weight average molecular weight of the entire mixture) is preferably 5000 to 500000. (A) The weight average molecular weight of the alkali-soluble polymer is preferably 5000 or more from the viewpoint of maintaining the thickness of the dry film resist to be uniform and obtaining resistance to a developer, and is preferably 500000 or less from the viewpoint of maintaining the developability of the dry film resist. (A) The weight average molecular weight of the alkali-soluble polymer is more preferably 10000 to 200000, and still more preferably 20000 to 100000. (A) The dispersion degree of the alkali-soluble polymer is preferably 1.0 to 6.0.
In the third embodiment, the content of the alkali-soluble polymer (a) in the photosensitive resin composition is preferably within a range of 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 40 to 60% by mass, based on the total solid content of the photosensitive resin composition (hereinafter, unless otherwise specified, the same applies to each component). (A) The content of the alkali-soluble polymer is preferably 10 mass% or more from the viewpoint of maintaining the alkali developability of the photosensitive resin layer, and is preferably 90 mass% or less from the viewpoint of sufficiently exhibiting the performance as a resist material of a resist pattern formed by exposure.
(B) Compounds containing ethylenic unsaturation
(B) The ethylenically unsaturated bond-containing compound is a compound having polymerizability by having an ethylenically unsaturated group in its structure. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group from the viewpoint of addition polymerizability.
In the third embodiment, when the alkali-soluble polymer (a) and the ethylenically unsaturated bond-containing compound (B) are used in combination, the weight average molecular weight of the ethylenically unsaturated bond-containing compound (B) is preferably 1200 or more from the viewpoint of ensuring the hole coverage of the resist pattern. In the present specification, with respect to the weight average molecular weight of the ethylenically unsaturated bond-containing compound (B), when the ethylenically unsaturated bond-containing compound (B) is a single one, it means a weight average molecular weight derived from the structural formula of the ethylenically unsaturated bond-containing compound of the single one, and when the ethylenically unsaturated bond-containing compound (B) is composed of a plurality of kinds, it means a weighted average of the weight average molecular weight of each ethylenically unsaturated bond-containing compound and the compounding ratio.
(B) The weight average molecular weight of the ethylenically unsaturated bond-containing compound is more preferably 1300 or more, and still more preferably 1400 or more from the viewpoint of further improving the hole-covering property of the resist pattern, and is more preferably 5000 or less, still more preferably 4000 or less, and particularly preferably 3000 or less from the viewpoint of the resolution and the peeling property of the resist pattern.
(B) The ethylenically unsaturated bond-containing compound may comprise a compound selected from the group consisting of (b)1)～(b5) At least 1 of the group consisting of:
(b1) An ethylene glycol di (meth) acrylate compound represented by the following general formula (I):
Figure BDA0003379849860000501
{ formula (II) wherein R1And R2Independently of one another, represent a hydrogen atom orMethyl, and m1The number of the particles is 2 to 40. };
(b2) An alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the following general formula (II):
Figure BDA0003379849860000502
{ formula (II) wherein R3And R4Independently of one another, represents a hydrogen atom or a methyl group, A is C2H4B is C3H6，n1、n2、n3And n4To satisfy n1+n2+n3+n4The arrangement of the repeating units of- (a-O) -and- (B-O) -may be random or block, and in the case of a block, any of- (a-O) -and- (B-O) -may be on the biphenyl side. };
(b3) A tri (meth) acrylate compound represented by the following general formula (III):
Figure BDA0003379849860000511
{ formula (II) wherein R5～R7Independently represents a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m2、m3And m4Independently of one another, m is an integer of 0 to 402+m3+m41 to 40, and m2+m3+m4In the case of 2 or more, X's are optionally the same as or different from each other };
(b4) A urethane di (meth) acrylate compound represented by the following general formula (IV):
Figure BDA0003379849860000512
{ formula (II) wherein R8And R9Independently represents a hydrogen atom or a methyl group, Y represents an alkylene group having 2 to 6 carbon atoms, and Z represents a di A divalent organic group, and s and t are each independently an integer of 0 to 40, and s + t is ≧ 1 }; and (b)5) In addition to the above (b)1)～(b4) Other addition polymerizable monomers.
The ethylenically unsaturated bond-containing compound (B) preferably contains (B) from the viewpoint of adjusting the peeling time of the resist pattern and the size of the peeled sheet1) An ethylene glycol di (meth) acrylate compound represented by the general formula (I).
In the general formula (I), m1The peeling time and the size of the peeling sheet are preferably 2 or more, and the resolution, plating resistance and etching resistance are preferably 40 or less. m is1More preferably 4 to 20, and still more preferably 6 to 12.
Specific examples of the ethylene glycol di (meth) acrylate compound represented by the general formula (I) are preferably m1Tetraethylene glycol di (meth) acrylate of 4, m19 nonaethylene glycol di (meth) acrylate, or m1Polyethylene glycol di (meth) acrylate of 14.
From the viewpoint of resolution and pore-capping ability, the (B) ethylenically unsaturated bond-containing compound preferably contains (B)2) An alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II). B in the general formula (II) may be-CH2CH2CH2-or-CH (CH)3)CH2-。
The hydrogen atom on the aromatic ring in the general formula (II) may be substituted with a hetero atom and/or a substituent.
Examples of the hetero atom include a halogen atom and the like, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a phenacyl group, an amino group, an alkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a nitro group, a cyano group, a carbonyl group, a mercapto group, an alkylmercapto group having 1 to 10 carbon atoms, an aryl group, a hydroxyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, an acyl group having 1 to 10 carbon atoms in the alkyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group or heterocyclic group having 2 to 10 carbon atoms, and an aryl group substituted with these substituents. These substituents may form a fused ring, or hydrogen atoms in these substituents may be substituted with hetero atoms such as halogen atoms. When the aromatic ring in the general formula (II) has a plurality of substituents, the plurality of substituents may be the same or different.
R in the general formula (II)3And R4Independently of each other, a hydrogen atom or a methyl group, and R is preferably R from the viewpoint of ensuring the contrast immediately after exposure of the photosensitive resin layer formed from the photosensitive resin composition 3And R4One or both of (a) and (b) are hydrogen atoms, more preferably R3And R4Both are hydrogen atoms.
From the viewpoint of porosity, (b) is preferred2) An alkylene oxide having a relatively long chain is added to the alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II). More specifically, in the general formula (II), n1、n2、n3And n4Preferably satisfies n1+n2+n3+n4More preferably, n is satisfied in the relationship of 4 to 501+n2+n3+n4More preferably, n satisfies the relationship of 10 to 501+n2+n3+n4In the relationship of 20 to 50, n is particularly preferably satisfied1+n2+n3+n4The relationship is 30 to 50.
From the viewpoint of porosity, (B) 40% by mass or more of the ethylenically unsaturated bond-containing compound (B) is preferably (B)2) The alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II) is more preferably n in the general formula (II)1、n2、n3And n4Satisfies n1+n2+n3+n4An alkylene oxide-modified bisphenol A type di (meth) acrylate compound having a relationship of 30 to 50. More preferably, 50% by mass, still more preferably 55% by mass or more, and most preferably 60% by mass of the ethylenically unsaturated bond-containing compound (B) is (B)2) An alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II).
As (b)2) Preferred specific examples of the alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II) include di (meth) acrylate of polyethylene glycol obtained by adding an average of 1 unit of ethylene oxide to each end of bisphenol A, di (meth) acrylate of polyethylene glycol obtained by adding an average of 2 units of ethylene oxide to each end of bisphenol A, di (meth) acrylate of polyethylene glycol obtained by adding an average of 5 units of ethylene oxide to each end of bisphenol A, di (meth) acrylate of polyethylene glycol obtained by adding an average of 7 units of ethylene oxide to each end of bisphenol A, di (meth) acrylate of polyalkylene glycol obtained by adding an average of 6 units of ethylene oxide and an average of 2 units of propylene oxide to each end of bisphenol A, di (meth) acrylate of polyalkylene glycol obtained by adding an average of 15 units of ethylene oxide to each end of bisphenol A, and mixtures thereof, And di (meth) acrylates of polyalkylene glycols obtained by adding an average of 15 units of ethylene oxide and an average of 2 units of propylene oxide to both ends of bisphenol a.
In the general formula (II), n is n from the viewpoint of resolution and water remaining short-circuit failure suppressing property1、n2、n3And n4Also preferably satisfies n1+n2+n3+n4Also, it is particularly preferable that n satisfies the relationship of 2 to 101+n2+n3+n4The relationship is 2-4.
From the viewpoint of compatibility between the pinhole property and the water remaining short-circuit failure suppressing property, it is particularly preferable that (B) the ethylenically unsaturated bond-containing compound contains n satisfying the condition of the general formula (II)1+n2+n3+n4(iii) 30 to 50 or a compound represented by the general formula (II) wherein R is3And R4A compound in which one or both of them are hydrogen atoms, and a compound of the general formula (II) satisfying n1+n2+n3+n42 to 10.
From the viewpoint of resolution and pore-capping ability, the (B) ethylenically unsaturated bond-containing compound preferably contains (B)3) A tri (meth) acrylate compound represented by the general formula (III). X in the general formula (III) may be an alkylene group having 2 to 6 carbon atoms, for example, -CH2CH2-、-CH2CH2CH2-、-CH(CH3)CH2-and the like.
From the viewpoint of porosity, (b)3) The tri (meth) acrylate compound represented by the formula (III) preferably has a relatively long chain alkylene oxide moiety. More specifically, in the general formula (III), m2+m3+m4Preferably 10 to 40, and more preferably 20 to 40.
As (b)3) Preferable specific examples of the tri (meth) acrylate compound represented by the general formula (III) include Ethylene Oxide (EO) -modified trimethylolpropane tri (meth) acrylate (average molar number of EO added: 10-40), Propylene Oxide (PO) -modified trimethylolpropane tri (meth) acrylate (PO average addition mole number: 10-40), and the like.
The ethylenically unsaturated bond-containing compound (B) preferably contains (B) from the viewpoint of porosity4) A urethane di (meth) acrylate compound represented by the general formula (IV).
In the general formula (IV), Z represents a divalent organic group, and may be, for example, an alkylene group having 1 to 10 carbon atoms, an alkylene oxide group having 2 to 10 carbon atoms, a divalent alicyclic group having 3 to 10 carbon atoms which may have a substituent, or the like.
In the general formula (IV), Y represents an alkylene group having 2 to 6 carbon atoms, and may be, for example, -CH2CH2-、-CH2CH2CH2-、-CH(CH3)CH2-and the like.
From the viewpoint of further improving the hole-covering property, it is also preferable that- (Y-O) in the general formula (IV)s-a partial sum- (Y-O)t-the moieties are independently of each other- (C)2H5O)-(C3H6O)9-replacing.
As (b)4) Preferable specific examples of the urethane di (meth) acrylate compound represented by the general formula (IV) include addition reaction products of a (meth) acrylic monomer having a hydroxyl group at the β -position and diisocyanate compounds such as isophorone diisocyanate, 2, 6-toluene diisocyanate, 2, 4-toluene diisocyanate and 1, 6-hexamethylene diisocyanate, and tris ((meth) acryloyloxy groupTetraethylene glycol isocyanate), hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, and EO, PO-modified urethane di (meth) acrylate. The EO represents ethylene oxide, and the EO-modified compound has an ethylene oxide-based block structure. Further, PO represents propylene oxide, and the PO-modified compound has a block structure of a propylene oxide group. Examples of the EO-modified urethane di (meth) acrylate include a product name "UA-11" manufactured by Ninghamura chemical industries, Ltd. Further, as the EO or PO modified urethane di (meth) acrylate, for example, a trade name "UA-13" manufactured by Nippon Komura chemical Co., Ltd. These can be used alone in 1 or a combination of 2 or more.
(B) The compound containing an ethylenically unsaturated bond may contain other than (b)1)～(b4) An addition polymerizable monomer other than the component (b)5) And (3) components.
As (b)5) The following substances may be mentioned as components:
except that (b)3) Tri (meth) acrylates other than the component (a), such as trimethylolpropane tri (meth) acrylate, ethoxylated glycerol tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate, etc.;
tetra (meth) acrylates such as ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, pentaerythritol (poly) alkoxy tetra (meth) acrylate, and the like;
penta (meth) acrylates such as dipentaerythritol penta (meth) acrylate and the like;
hexa (meth) acrylates such as dipentaerythritol hexa (meth) acrylate, hexa (meth) acrylate obtained by adding ethylene oxide to 6 ends of dipentaerythritol by a total amount of 1 to 24 moles, hexa (meth) acrylate obtained by adding epsilon-caprolactone to 6 ends of dipentaerythritol by a total amount of 1 to 10 moles, and the like;
an acrylate compound having 1 (meth) acryloyl group;
a compound obtained by reacting a polyhydric alcohol with an α, β -unsaturated carboxylic acid;
A compound obtained by reacting a glycidyl group-containing compound with an α, β -unsaturated carboxylic acid; and
phthalic acid-based compounds such as γ -chloro-2-hydroxypropyl- β '- (meth) acryloyloxyethyl-phthalate and β -hydroxyalkyl- β' - (meth) acryloyloxyalkyl-phthalate, and the like.
In the third embodiment, the total content of all the ethylenically unsaturated bond-containing compounds (B) in the photosensitive resin composition is preferably in the range of 1 to 70% by mass, more preferably 2 to 60% by mass, and even more preferably 4 to 50% by mass, from the viewpoint of the hole coverage and adhesion of the resist pattern.
(C) Photopolymerization initiator
(C) The photopolymerization initiator is a compound that polymerizes monomers using light. The photosensitive resin composition contains a compound known in the art as a photopolymerization initiator.
The content of the photopolymerization initiator (C) in the photosensitive resin composition is preferably in the range of 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and still more preferably 0.1 to 7% by mass. (C) The content of the photopolymerization initiator is preferably 0.01% by mass or more in view of obtaining sufficient sensitivity, and is preferably 20% by mass or less in view of sufficiently transmitting light to the bottom surface of the resist to obtain good high resolution.
Examples of the photopolymerization initiator (C) include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkyl aminobenzoates, oxime esters, acridines, hexaarylbiimidazole, pyrazoline compounds, N-arylamino acids or ester compounds thereof (e.g., N-phenylglycine), organic halogen compounds, and the like. These can be used alone in 1 or a combination of 2 or more. Among them, acridines are particularly suitable for direct imaging exposure.
Examples of the acridines include acridine derivatives such as acridine, 9-phenylacridine, 1, 6-bis (9-acridinyl) hexane, 1, 7-bis (9-acridinyl) heptane, 1, 8-bis (9-acridinyl) octane, 1, 9-bis (9-acridinyl) nonane, 1, 10-bis (9-acridinyl) decane, 1, 11-bis (9-acridinyl) undecane, and 1, 12-bis (9-acridinyl) dodecane. From the viewpoint of suitability for direct image exposure, the content of acridines in the photosensitive resin composition is preferably in the range of 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, and still more preferably 0.5 to 2% by mass.
Examples of the aromatic ketone include benzophenone, michaelis-ler's ketone [4, 4' -bis (dimethylamino) benzophenone ], 4 '-bis (diethylamino) benzophenone, and 4-methoxy-4' -dimethylamino benzophenone. These can be used alone in 1 or a combination of 2 or more. Among them, from the viewpoint of adhesion, 4' -bis (diethylamino) benzophenone is preferable. Further, from the viewpoint of transmittance, the content of the aromatic ketone in the photosensitive resin composition is preferably in the range of 0.01 to 0.5 mass%, more preferably 0.02 to 0.3 mass%.
Examples of the hexaarylbiimidazole include 2- (o-chlorophenyl) -4, 5-diphenylbiimidazole, 2 ', 5-tris- (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4', 5 '-diphenylbiimidazole, 2, 4-bis- (o-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -diphenylbiimidazole, 2,4, 5-tris- (o-chlorophenyl) -diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4, 5- (3, 4-dimethoxyphenyl) -biimidazole, 2' -bis- (2-fluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -biimidazole, 2,2 ' -bis- (2, 3-difluoromethylphenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2, 4-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2, 5-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2, 6-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2,3, 4-trifluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 '-bis- (2,3, 5-trifluorophenyl) -4, 4', 5,5 '-tetrakis- (3-methoxyphenyl) -biimidazole, 2' -bis- (2,3, 6-trifluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 '-bis- (2,4, 5-trifluorophenyl) -4, 4', 5,5 '-tetrakis- (3-methoxyphenyl) -biimidazole, 2' -bis- (2,4, 6-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2,3,4, 5-tetrafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2,3,4, 6-tetrafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, and 2,2 ' -bis- (2,3,4,5, 6-pentafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, and the like, and 1 kind or more thereof may be used alone or 2 or more kinds may be used in combination. From the viewpoint of high sensitivity, resolution and adhesion, 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer is preferable.
In the third embodiment, the content of the hexaarylbiimidazole compound in the photosensitive resin composition is preferably in the range of 0.05 to 7 mass%, more preferably 0.1 to 6 mass%, and even more preferably 1 to 4 mass%, from the viewpoint of improving the peeling property and/or sensitivity of the photosensitive resin layer.
Examples of the N-aryl amino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, and the like. Among them, N-phenylglycine is particularly preferable. From the viewpoint of improving the peeling property and/or sensitivity, the content of the N-arylamino acid in the photosensitive resin composition is preferably 0.05 to 5% by mass, more preferably 0.1 to 2% by mass, relative to the total solid content of the photosensitive resin composition.
Examples of the organic halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, dibromomethane, tribromomethylphenylsulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1, 1-trichloro-2, 2-bis (p-chlorophenyl) ethane, and chlorotriazine compounds, and among them, tribromomethylphenylsulfone is particularly preferably used. From the viewpoint of improving the peeling property and/or sensitivity, the content of the organic halogen compound in the photosensitive resin composition is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, relative to the total amount of solid components of the photosensitive resin composition.
Examples of the other photosensitizers include 2-ethylanthraquinone, octaethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-benzoanthraquinone, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2-methyl-1, 4-naphthoquinone, 2, 3-dimethylanthraquinone, and oxime esters such as quinones such as 3-chloro-2-methylanthraquinone, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, benzoin ethers such as ethylbenzoin, benzildimethylketal, benzildiethylketal, 1-phenyl-1, 2-propanedione-2-O-benzoyl oxime, and 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime. From the viewpoint of improving the peeling property and/or sensitivity, the content of the photosensitizer in the photosensitive resin composition is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, relative to the total amount of solid components of the photosensitive resin composition.
In the third embodiment, the photosensitive resin composition preferably contains a pyrazoline compound as a photosensitizer. As the pyrazoline compound, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline, and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline are preferable.
(D) Additive agent
The photosensitive resin composition may contain additives such as a color-changing agent, a dye, a plasticizer, an antioxidant, and a stabilizer, as desired. For example, additives listed in Japanese patent laid-open publication No. 2013-156369 and International publication No. 2009/093706 may be used.
Examples of the color-changing agent include leuco dyes and fluoran dyes. The use of the color-changing agent is preferable in view of visibility based on color development of an exposed portion. Further, when an inspection machine or the like reads a positioning mark used for exposure, it is advantageous that the position is easily recognized when the contrast between an exposed portion and an unexposed portion is large.
Examples of leuco dyes include tris (4-dimethylaminophenyl) methane [ leuco crystal violet ], bis (4-dimethylaminophenyl) phenylmethane [ leuco malachite green ], and the like. In particular, leuco crystal violet is preferably used as the leuco dye from the viewpoint of good contrast. The content of the leuco dye in the photosensitive resin composition is preferably 0.1 to 10% by mass. The content thereof is preferably 0.1% by mass or more from the viewpoint of contrast between an exposed portion and an unexposed portion, and is preferably 10% by mass or less from the viewpoint of maintaining storage stability.
Examples of the basic dye include basic green 1[ CAS number (the same applies below): 633-03-4] (e.g., Aizen Diamond Green GH, trade name, manufactured by Baotou chemical industries, Ltd.), Malachite Green oxalate [2437-29-8] (e.g., Aizen Malachite Green, trade name, manufactured by Baotou chemical industries, Ltd.), brilliant Green [633-03-4], fuchsin [632-99-5], methyl violet [603-47-4], methyl violet 2B [8004-87-3], crystal violet [548-62-9], methyl Green [82-94-0], Victoria Blue B [2580-56-5], basic Blue 7[2390-60-5] (e.g., Aizen Victoria Pure Blue BOH, trade name, manufactured by Baoto chemical industries, Ltd.), rhodamine B [81-88-9] (Hadamia, Rhodamine 6G [989-38-8], basic yellow 2[2465-27-2] and the like. Among them, basic green 1, malachite green oxalate, and basic blue 7 are preferable, and basic green 1 is particularly preferable from the viewpoint of improving the color stability and the exposure contrast.
In the third embodiment, the content of the basic dye in the photosensitive resin composition is preferably in the range of 0.001 to 3% by mass, more preferably 0.01 to 2% by mass, and still more preferably 0.01 to 1% by mass. The content of the dye is preferably 0.001 mass% or more from the viewpoint of obtaining good coloring property, and is preferably 3 mass% or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.
In the third embodiment, in order to suppress the delay of resist pattern peeling and shorten the peeling time due to the alkali-soluble polymer having a content of a structural unit of (meth) acrylic acid of 10 to 24 mass%, it is preferable that a toluene sulfonic acid amide such as o-toluene sulfonic acid amide or p-toluene sulfonic acid amide is contained as a plasticizer in the photosensitive resin composition. The content of the tosylamide in the photosensitive resin composition is preferably in the range of 0.1 to 5% by mass, more preferably 1 to 4% by mass.
Examples of the other plasticizer include glycol esters such as polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, and polyoxyethylene polyoxypropylene monoethyl ether; phthalic acid esters such as diethyl phthalate; tributyl citrate, triethyl citrate, acetyl tri-n-propyl citrate, and acetyl tri-n-butyl citrate; propylene glycol obtained by adding propylene oxide to each side of bisphenol a, ethylene glycol obtained by adding ethylene oxide to each side of bisphenol a, and the like.
From the viewpoint of thermal stability or storage stability of the photosensitive resin composition, the photosensitive resin composition preferably contains, as a stabilizer, at least one selected from the group consisting of: radical polymerization inhibitors such as p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, 2, 6-di-t-butyl-p-cresol, 2 '-methylenebis (4-methyl-6-t-butylphenol), 2' -methylenebis (4-ethyl-6-t-butylphenol), diphenylnitrosamine, triethylene glycol-bis (3-3-t-butyl-5-methyl-4-hydroxyphenyl propionate), and nitrosophenylhydroxylamine aluminum salt; benzotriazoles such as 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-tolyltriazole, 1- (2-di-N-octylaminomethyl) -benzotriazole, and bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole; carboxybenzotriazoles, for example, 1: 1 mixture, N- (N, N-di-2-ethylhexyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole, and the like; and alkylene oxide compounds having a glycidyl group such as neopentyl glycol diglycidyl ether (for example, Eplight 1500NP manufactured by Kyoeisha chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (for example, Eplight 400E manufactured by Kyoeisha chemical Co., Ltd.), bisphenol A-propylene oxide 2 molar adduct diglycidyl ether (for example, Eplight 3002 manufactured by Kyoeisha chemical Co., Ltd.), hydrogenated bisphenol A diglycidyl ether (for example, Eplight 4000 manufactured by Kyoeisha chemical Co., Ltd.), 1, 6-hexanediol diglycidyl ether (for example, Eplight 1600 manufactured by Kyoeisha chemical Co., Ltd.), and the like.
In the third embodiment, the total content of all the stabilizers in the photosensitive resin composition is preferably in the range of 0.001 to 3% by mass, more preferably 0.01 to 1% by mass, and still more preferably 0.05 to 0.7% by mass. The total content of the stabilizer is preferably 0.001 mass% or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably 3 mass% or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.
The above-mentioned additives may be used singly in 1 kind or in combination in 2 or more kinds.
< photosensitive resin composition preparation liquid >
In the third embodiment, a photosensitive resin composition preparation liquid can be formed by adding a solvent to a photosensitive resin composition. Suitable solvents include ketones such as acetone, Methyl Ethyl Ketone (MEK), and the like; and alcohols such as methanol, ethanol, isopropanol, and the like. The solvent is preferably added to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid is 500 to 4000mPa · s at 25 ℃.
< photosensitive resin laminate >
In the third embodiment, a photosensitive resin laminate having a support and a photosensitive resin layer formed of the photosensitive resin composition and laminated on the support can be provided. The photosensitive resin laminate may have a protective layer on the side of the photosensitive resin layer opposite to the support body side as desired.
The support is not particularly limited, and is preferably a transparent support that transmits light emitted from the exposure light source. Examples of such a support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. These films may also be stretched as desired. The haze is preferably 0.01% to 5.0%, more preferably 0.01% to 2.5%, and further preferably 0.01% to 1.0%. The thinner the film thickness is, the more advantageous the image formability and the economical efficiency is, but the strength needs to be maintained, and therefore, it is preferably 10 μm to 30 μm.
In addition, an important characteristic of the protective layer used in the photosensitive resin laminate is that the adhesion force between the protective layer and the photosensitive resin layer is small compared to the adhesion force between the support and the photosensitive resin layer, and the protective layer can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film, or the like is preferable. For example, a film excellent in releasability as disclosed in Japanese patent application laid-open No. 59-202457 can be used. The thickness of the protective layer is preferably 10 to 100 μm, more preferably 10 to 50 μm.
In the third embodiment, the thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 5 μm to 100 μm, and more preferably 7 μm to 60 μm. The smaller the thickness of the photosensitive resin layer, the higher the resolution of the resist pattern, while the larger the thickness of the photosensitive resin layer, the higher the strength of the cured film, and therefore, it can be selected according to the application.
As a method for producing a photosensitive resin laminate by sequentially laminating a support, a photosensitive resin layer, and a desired protective layer, a known method can be used.
For example, the photosensitive resin composition preparation liquid is prepared, and then applied to a support by using a bar coater or a roll coater and dried, and a photosensitive resin layer formed from the photosensitive resin composition preparation liquid is laminated on the support. Further, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer as desired.
< method for forming resist pattern >
The method of forming a resist pattern preferably includes, in order: a laminating step of laminating a photosensitive resin layer formed of the photosensitive resin composition on a support, an exposure step of exposing the photosensitive resin layer, and a development step of developing the exposed photosensitive resin layer. In the third embodiment, an example of a specific method for forming a resist pattern is shown below.
First, in the laminating step, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the photosensitive resin layer is heated and pressed against the surface of the substrate by a laminator after the protective layer is peeled off, and the laminate is laminated. Examples of the material of the substrate include copper, stainless steel (SUS), glass, and Indium Tin Oxide (ITO).
In the third embodiment, the photosensitive resin layer may be laminated on only one surface of the substrate surface or may be laminated on both surfaces as necessary. The heating temperature for lamination is usually 40 to 160 ℃. Further, by performing the heat pressure bonding at the time of lamination 2 times or more, the adhesion of the obtained resist pattern to the substrate can be improved. In the case of thermal pressure bonding, a two-stage laminator provided with two or more rollers may be used, or pressure bonding may be performed by passing a laminate of the substrate and the photosensitive resin layer through the rollers several times.
Next, in the exposure step, the photosensitive resin layer is exposed to active light using an exposure machine. The exposure may be performed after peeling off the support as desired. When exposure is performed through a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time, and can be measured using a light meter. In the exposure step, direct image exposure may be performed. In direct imaging exposure, exposure is performed on a substrate by a direct writing apparatus without using a photomask. As the light source, a semiconductor laser or an ultra-high pressure mercury lamp having a wavelength of 350nm to 410nm is used. When the pattern is drawn by a computer, the exposure amount is determined by the illuminance of the exposure light source and the moving speed of the substrate.
Next, in the developing step, the unexposed portion or the exposed portion of the exposed photosensitive resin layer is removed using a developing solution for a developing device. After exposure, when the support is present on the photosensitive resin layer, the support is removed. Next, the unexposed portion or the exposed portion is developed and removed using a developer solution containing an alkali aqueous solution, thereby obtaining a resist image.
As the aqueous alkali solution, Na is preferred2CO3、K2CO3And the like. The alkali aqueous solution is selected according to the characteristics of the photosensitive resin layer, and Na is usually used in a concentration of 0.2 to 2 mass%2CO3An aqueous solution. The aqueous alkali solution may contain a surfactant, a defoaming agent, a small amount of an organic solvent for promoting development, and the like. The temperature of the developing solution in the developing step is preferably kept constant within a range of 20 to 40 ℃.
The above-described steps can provide a resist pattern, and if desired, the heating step may be further performed at 100 to 300 ℃. By performing this heating step, the chemical resistance of the resist pattern can be improved. In the heating step, a heating furnace using a hot air, infrared ray, or far infrared ray system may be used.
The photosensitive resin composition of the third embodiment can be suitably used for forming a circuit of a printed board. Generally, as a circuit forming method of a printed substrate, a subtractive method and a semi-additive method (SAP) are used.
The subtractive method is a method of forming a circuit by removing only a non-circuit portion from a conductor disposed on the entire surface of a substrate by etching.
The SAP is a method of forming only a circuit portion by plating after forming a resist on a non-circuit portion disposed on a conductor seed layer over the entire surface of a substrate.
< method for manufacturing conductor pattern >
The method for manufacturing the conductor pattern preferably includes, in order: a laminating step of laminating a photosensitive resin layer formed of the photosensitive resin composition on a substrate such as a metal plate or a metal-coated insulating plate; an exposure step of exposing the photosensitive resin layer; a developing step of removing the unexposed portion or the exposed portion of the exposed photosensitive resin layer with a developing solution to obtain a substrate on which a resist pattern is formed; and a conductor pattern forming step of etching or plating the substrate on which the resist pattern is formed.
In the third embodiment, the method for manufacturing the conductor pattern is performed as follows: the substrate is formed by using a metal plate or a metal-coated insulating plate, forming a resist pattern by the above-described resist pattern forming method, and then performing a conductor pattern forming step. In the conductive pattern forming step, a conductive pattern is formed on the surface (for example, copper surface) of the substrate exposed by the development by a known etching method or plating method.
The third embodiment is applied to the following applications, for example.
< method for manufacturing circuit board >
After the conductor pattern is produced by the method for producing a conductor pattern, a step of peeling the resist pattern from the substrate with an aqueous solution having an alkali stronger than that of the developer is further performed, whereby a circuit board (for example, a printed circuit board) having a desired wiring pattern can be obtained.
The alkaline aqueous solution for stripping (hereinafter also referred to as "stripping solution") is not particularly limited, and an aqueous solution of NaOH or KOH having a concentration of 2 to 5 mass%, or an organic amine-based stripping solution is usually used. A small amount of a water-soluble solvent may be added to the stripping solution. Examples of the water-soluble solvent include alcohols. The temperature of the stripping solution in the stripping step is preferably in the range of 40 to 70 ℃.
< manufacturing of lead frame >
A metal plate of copper, a copper alloy, an iron alloy, or the like is used as a substrate, a resist pattern is formed by a resist pattern forming method, and then the following steps are performed to manufacture a lead frame. First, a step of forming a conductor pattern by etching the substrate exposed by development is performed. Then, a peeling step of peeling the resist pattern is performed by the same method as the method for manufacturing the circuit board, and a desired lead frame can be obtained.
< production of substrate having uneven Pattern >
The resist pattern formed by the resist pattern forming method can be used as a protective mask member for processing a substrate by a sand blast method. In this case, examples of the substrate include glass, silicon wafer, amorphous silicon, polycrystalline silicon, ceramic, sapphire, and a metal material. A resist pattern is formed on these substrates by the same method as the resist pattern forming method. Then, a blast treatment step of blowing a blast from above the formed resist pattern to cut the resist pattern to a target depth and a peeling step of removing the resist pattern portion remaining on the substrate from the substrate with an alkali peeling liquid or the like are performed, whereby a base material having a fine uneven pattern on the substrate can be produced.
In the blasting step, a known blasting agent can be used, and for example, a material containing SiC or SiO is usually used2、Al2O3、CaCO3Fine particles of 2 to 100 μm in particle diameter such as ZrO, glass and stainless steel.
< manufacture of semiconductor Package >
A wafer on which a large scale integrated circuit (LSI) is formed is used as a substrate, and after a resist pattern is formed on the wafer by a resist pattern forming method, a semiconductor package can be manufactured through the following steps. First, a step of forming a conductor pattern by applying columnar plating of copper, solder, or the like to the opening exposed by development is performed. Then, a desired semiconductor package can be obtained by performing a peeling step of peeling the resist pattern by the same method as the method of manufacturing the circuit board, and further performing a step of removing the thin metal layer in the portion other than the columnar plating by etching.
In the third embodiment, the photosensitive resin composition can be used for the production of printed wiring boards; manufacturing a lead frame for mounting an IC chip; metal foil precision processing such as metal mask manufacturing; manufacturing packages such as Ball Grid Arrays (BGAs) and Chip Scale Packages (CSPs); manufacturing a tape substrate such as a Chip On Film (COF) and a Tape Automated Bonding (TAB); manufacturing a semiconductor bump; and the manufacture of partition walls for flat panel displays such as ITO electrodes, address electrodes, and electromagnetic wave shields.
The values of the parameters are measured by the measurement method in the examples described below, unless otherwise specified.
< fourth embodiment >
Hereinafter, a mode for carrying out the fourth embodiment of the present invention (hereinafter, simply referred to as "the present fourth embodiment") will be specifically described.
< photosensitive resin composition >
In the fourth embodiment, the photosensitive resin composition contains (a) an alkali-soluble polymer, (B) an ethylenically unsaturated bond-containing compound, and (C) a photopolymerization initiator. The photosensitive resin composition further contains (D) other components such as a stabilizer, as desired.
In the present specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid, "(meth) acryloyl group" means acryloyl group or methacryloyl group, and "(meth) acrylate" means "acrylate" or "methacrylate".
[ (A) alkali-soluble Polymer ]
The alkali-soluble polymer (a) contains a first copolymer having a content ratio of acid monomer units of less than 25 mass% and a content ratio of aromatic monomer units of 30 mass% or more, from the viewpoint of extending resolution and minimum development time. The first copolymer may also contain other monomer units in addition to the acid monomer units and the aromatic monomer units as desired. The degree of dispersion of the copolymer, which is expressed by the ratio of the weight average molecular weight (described later) to the number average molecular weight of the copolymer, is preferably 1 to 6.
Examples of the acid monomer include (meth) acrylic acid, pentenoic acid, unsaturated dicarboxylic anhydride, and hydroxystyrene. Examples of the unsaturated dicarboxylic anhydride include maleic anhydride, itaconic anhydride, fumaric acid, and citraconic anhydride. Among them, (meth) acrylic acid is preferable.
The copolymerization ratio of the acid monomer units in the component (a) is preferably less than 25% by mass, more preferably 10% by mass to 24% by mass, and still more preferably 15% by mass to 23% by mass, based on the total mass of all the monomer units. When the content ratio of the acid monomer unit is within this range, it is preferable from the viewpoint of improvement in resolution and extension of the minimum development time.
Aromatic monomers are also referred to as unsaturated aromatic compounds. Examples of the aromatic monomer include styrene, α -methylstyrene, vinylnaphthalene, and the like; aralkyl (meth) acrylates, and the like. Examples of the aralkyl (meth) acrylate include benzyl (meth) acrylate and the like.
The copolymerization ratio of the aromatic monomer unit (preferably styrene unit) in the component (a) is preferably 30% by mass or more, more preferably 32% by mass to 60% by mass, and still more preferably 35% by mass to 55% by mass, based on the total mass of all monomer units. When the copolymerization ratio of the aromatic monomer having high hydrophobicity and being difficult to be compatible with the developer and the developing cleaning water is set to the above range, it is preferable from the viewpoint of improvement of resolution and extension of minimum developing time.
Examples of the other monomer include an alkyl (meth) acrylate, a conjugated diene compound, a polar monomer, and a crosslinkable monomer.
The alkyl (meth) acrylate is a concept including both a chain alkyl ester and a cyclic alkyl ester, and specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, n-tetradecyl (meth) acrylate, stearyl (meth) acrylate, and cyclohexyl (meth) acrylate.
Examples of the conjugated diene compound include 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 2-phenyl-1, 3-butadiene, 1, 3-pentadiene, 2-methyl-1, 3-pentadiene, 1, 3-hexadiene, 4, 5-diethyl-1, 3-octadiene, and 3-butyl-1, 3-octadiene.
Examples of the polar monomer include:
hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and pentenol; amino group-containing monomers such as 2-aminoethyl methacrylate;
amide group-containing monomers such as (meth) acrylamide and N-methylol (meth) acrylamide;
cyano group-containing monomers such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, and α -cyanoethylacrylate;
epoxy group-containing monomers such as glycidyl (meth) acrylate and 3, 4-epoxycyclohexyl (meth) acrylate;
and the like.
Examples of the crosslinkable monomer include trimethylolpropane triacrylate and divinylbenzene.
The aforementioned first copolymer is particularly preferably a copolymer of (meth) acrylic acid, styrene, and other monomers.
In the fourth embodiment, the second copolymer containing the aromatic monomer unit described above at a content ratio of 45 to 90 mass% is also preferable from the viewpoint of resolution, developability, and aggregability. The content ratio of the aromatic monomer unit in the second copolymer is 45% by mass, and thus the hydrophobicity of the resist pattern including the second copolymer tends to be secured. In addition, when the weight ratio of the second copolymer is 25% by mass or more based on the total weight of the entire copolymer, it is preferable from the viewpoint of improving the aggregation property.
The second copolymer may also comprise the acid monomer units and other monomer units as described above. As the aromatic monomer for polymerizing the second copolymer, styrene is preferable from the viewpoint of hydrophobicity. From the viewpoint of developability, the upper limit of the content ratio of the aromatic monomer unit in the second copolymer is more preferably 80% by mass or 70% by mass.
The second copolymer may contain the above-described acid monomer unit and other monomer units, and the content ratio of the above-described acid monomer unit is preferably 25 to 50% by mass, more preferably 25 to 40% by mass, from the viewpoint of resolution, developability, and aggregability. As the acid monomer for polymerizing the second copolymer, (meth) acrylic acid is preferable from the viewpoint of developability.
The weight average molecular weight of the component (A) (when the component (A) includes a plurality of copolymers, the weight average molecular weight of the whole mixture) is preferably 5000 to 1000000, more preferably 10000 to 500000, and still more preferably 15000 to 100000. When the weight average molecular weight of the component (a) is adjusted within this range, it is preferable from the viewpoint of adapting the development time at the time of resist pattern formation to the running state of the line used.
In the fourth embodiment, the content of the component (a) in the photosensitive resin composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 40 to 60% by mass based on the total solid content of the photosensitive resin composition (hereinafter, the same applies to each component contained unless otherwise specified). The content is preferably 10 mass% or more from the viewpoint of maintaining alkali developability, and is preferably 90 mass% or less from the viewpoint of sufficiently exerting the performance as a resist of a resist pattern formed by exposure.
The first copolymer having a content of the acid monomer unit of less than 25% by mass and a content of the aromatic monomer unit of 30% by mass or more is preferably 5% by mass or more and 50% by mass or less based on the total solid content of the photosensitive resin composition. More preferably 10 to 40 mass%.
[ (B) Compounds containing ethylenic unsaturation ]
(B) The ethylenically unsaturated bond-containing compound is a compound having polymerizability by having an ethylenically unsaturated group in its structure. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group from the viewpoint of addition polymerizability.
In the fourth embodiment, when (a) the alkali-soluble polymer and (B) the ethylenically unsaturated bond-containing compound are used in combination, the weight average molecular weight of the ethylenically unsaturated bond-containing compound (B) is preferably 900 or less from the viewpoint of ensuring good resolution of the resist pattern and extending the minimum development time. In the present specification, with respect to the average molecular weight of the ethylenically unsaturated bond-containing compound (B), when the ethylenically unsaturated bond-containing compound (B) is a single one, it means a weight average molecular weight derived from the structural formula of the ethylenically unsaturated bond-containing compound of the single one, and when the ethylenically unsaturated bond-containing compound (B) is composed of a plurality of kinds, it means a weighted average of the weight average molecular weight of each ethylenically unsaturated bond-containing compound and the compounding ratio.
(B) The weight average molecular weight of the ethylenically unsaturated bond-containing compound is more preferably 850 or less, and still more preferably 800 or less from the viewpoint of improvement in resolution and extension of the minimum development time, and is preferably 50 or more, and more preferably 100 or more from the viewpoint of suppressing the edge fusibility of the photosensitive resin laminate. Here, the edge fusibility is a phenomenon in which the photosensitive resin composition layer bleeds out from the end face of the roll when the photosensitive resin laminate is wound into a roll.
(B) The ethylenically unsaturated bond-containing compound may comprise a compound selected from the group consisting of (b)1)～(b6) At least 1 of the group consisting of:
(b1) An ethylene glycol di (meth) acrylate compound represented by the following general formula (I):
Figure BDA0003379849860000691
{ formula (II) wherein R1And R2Independently of one another, represents a hydrogen atom or a methyl group, and m1The number of the particles is 2 to 40. };
(b2) An alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the following general formula (II):
Figure BDA0003379849860000692
{ formula (II) wherein R3And R4Independently of one another, represents a hydrogen atom or a methyl group, A is C2H4B is C3H6，n1、n2、n3And n4To satisfy n1+n2+n3+n4The arrangement of the repeating units of- (a-O) -and- (B-O) -may be random or block, and in the case of a block, any of- (a-O) -and- (B-O) -may be on the biphenyl side. };
(b3) A tri (meth) acrylate compound represented by the following general formula (III):
Figure BDA0003379849860000693
{ formula (II) wherein R5～R7Independently represents a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m2、m3And m4Independently of one another, m is an integer of 0 to 402+m3+m40 to 40, and m2+m3+m4In the case of 2 or more, X's are optionally the same as or different from each other };
(b4) A urethane di (meth) acrylate compound represented by the following general formula (IV):
Figure BDA0003379849860000701
{ formula (II) wherein R8And R9Independently represents a hydrogen atom or a methyl group, Y represents an alkylene group having 2 to 6 carbon atoms, Z represents a divalent organic group, and s and t are independently integers of 0 to 40, and s + t.gtoreq.1 };
(b5) A tetra (meth) acrylate compound represented by the following general formula (XI):
Figure BDA0003379849860000702
{ formula (II) wherein R5～R8Independently represents a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m2、m3、m4And m5Independently of one another, m is an integer of 0 to 402+m3+m4+m50 to 50, and m2+m3+m4+m5In the case of 2 or more, X's are optionally the same as or different from each other }; and
(b6) In addition to the above (b)1)～(b5) Other addition polymerizable monomers.
The ethylenically unsaturated bond-containing compound (B) preferably contains (B) from the viewpoint of adjusting the peeling time of the resist pattern and the size of the peeled sheet1) An ethylene glycol di (meth) acrylate compound represented by the general formula (I).
In the general formula (I), m1The peeling time and the size of the peeling sheet are preferably 2 or more, and the resolution, plating resistance and etching resistance are preferably 40 or less. m is1More preferably 4 to 20, and still more preferably 6 to 12.
Specific examples of the ethylene glycol di (meth) acrylate compound represented by the general formula (I) are preferably m1Tetraethylene glycol di (meth) acrylate of 4, m19 nonaethylene glycol di (meth) acrylate, or m1Polyethylene glycol di (meth) acrylate of 14.
The ethylenically unsaturated bond-containing compound (B) preferably contains (B) from the viewpoint of suppressing generation of aggregates at the time of development of a photosensitive resin layer formed from the photosensitive resin composition 2) An alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II). B in the general formula (II) may be-CH2CH2CH2-or-CH (CH)3)CH2-。
The hydrogen atom on the aromatic ring in the general formula (II) may be substituted with a hetero atom and/or a substituent.
Examples of the hetero atom include a halogen atom and the like, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a phenacyl group, an amino group, an alkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a nitro group, a cyano group, a carbonyl group, a mercapto group, an alkylmercapto group having 1 to 10 carbon atoms, an aryl group, a hydroxyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, an acyl group having 1 to 10 carbon atoms in the alkyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group or heterocyclic group having 2 to 10 carbon atoms, and an aryl group substituted with these substituents. These substituents may form a fused ring, or hydrogen atoms in these substituents may be substituted with hetero atoms such as halogen atoms. When the aromatic ring in the general formula (II) has a plurality of substituents, the plurality of substituents may be the same or different.
R in the general formula (II)3And R4Independently of each other, a hydrogen atom or a methyl group, and R is preferably R from the viewpoint of ensuring the contrast immediately after exposure of the photosensitive resin layer formed from the photosensitive resin composition3And R4One or both of (a) and (b) are hydrogen atoms, more preferably R3And R4Both are hydrogen atoms.
From the viewpoints of improvement in resolution and extension of minimum development time, (b) is preferable2) A relatively short-chain alkylene oxide is added to the alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II). More specifically, in the general formula (II), n1、n2、n3And n4Preferably satisfies n1+n2+n3+n4More preferably, n is satisfied in the range of 0 to 301+n2+n3+n4Preferably, n is 0 to 251+n2+n3+n4The relationship of 0 to 20, particularly preferably n1+n2+n3+n40 to 10.
From the viewpoint of improving resolution and extending the minimum development time, it is preferable that 40% by mass or more of (B) the ethylenically unsaturated bond-containing compound is (B)2) An alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II), more preferably n in the general formula (II)1、n2、n3And n4Satisfies n1+n2+n3+n4An alkylene oxide-modified bisphenol A type di (meth) acrylate compound having a relationship of 0 to 20. More preferably, 50% by mass, still more preferably 55% by mass or more, and most preferably 60% by mass of the ethylenically unsaturated bond-containing compound (B) is (B) 2) An alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II).
As (b)2) Preferred specific examples of the alkylene oxide-modified bisphenol a type di (meth) acrylate compound represented by the general formula (II) include di (meth) acrylate of polyethylene glycol obtained by adding an average of 1 unit of ethylene oxide to each end of bisphenol a, di (meth) acrylate of polyethylene glycol obtained by adding an average of 2 units of ethylene oxide to each end of bisphenol a, di (meth) acrylate of polyethylene glycol obtained by adding an average of 5 units of ethylene oxide to each end of bisphenol a, di (meth) acrylate of polyethylene glycol obtained by adding an average of 7 units of ethylene oxide to each end of bisphenol a, di (meth) acrylate of polyalkylene glycol obtained by adding an average of 6 units of ethylene oxide and an average of 2 units of propylene oxide to each end of bisphenol a, and di (meth) acrylate of polyalkylene glycol obtained by adding an average of 15 units of ethylene oxide to each end of bisphenol a And di (meth) acrylates of polyalkylene glycols obtained by adding an average of 15 units of ethylene oxide and an average of 2 units of propylene oxide to both ends of bisphenol a.
In the general formula (II), n is n from the viewpoint of improving resolution1、n2、n3And n4Also preferably satisfies n1+n2+n3+n4Also, it is particularly preferable that n satisfies the relationship of 2 to 201+n2+n3+n4The relationship is 2-10.
From the viewpoints of improvement in resolution and prolongation of minimum development time, it is particularly preferable that (B) the ethylenically unsaturated bond-containing compound andthe method comprises the following steps: n in the general formula (II)1+n2+n3+n4A compound of the formula (II) wherein R is 2 to 203And R4A compound wherein one or both of them are methyl, and a compound represented by the general formula (II)1+n2+n3+n42 to 16.
The ethylenically unsaturated bond-containing compound (B) preferably contains (B) from the viewpoint of suppressing generation of aggregates at the time of development of a photosensitive resin layer formed from the photosensitive resin composition3) A tri (meth) acrylate compound represented by the general formula (III). X in the general formula (III) is an alkylene group having 2 to 6 carbon atoms, and may be, for example, -CH2CH2-、-CH2CH2CH2-、-CH(CH3)CH2-and the like.
From the viewpoint of resolution, (b)3) The tri (meth) acrylate compound represented by the formula (III) preferably has a shorter chain of alkylene oxide moieties. More specifically, in the general formula (III), m2+m3+m4Preferably 8 to 40, and more preferably 9 to 25.
As (b)3) Preferable specific examples of the tri (meth) acrylate compound represented by the general formula (III) include Ethylene Oxide (EO) -modified trimethylolpropane tri (meth) acrylate (average molar number of EO added: 1 to 40), Propylene Oxide (PO) -modified trimethylolpropane tri (meth) acrylate (PO average addition mole number: 1-40), and the like.
From the viewpoint of resolution, the (B) ethylenically unsaturated bond-containing compound preferably contains (B)4) A urethane di (meth) acrylate compound represented by the general formula (IV).
In the general formula (IV), Z represents a divalent organic group, and may be, for example, an alkylene group having 1 to 10 carbon atoms, an alkylene oxide group having 2 to 10 carbon atoms, a divalent alicyclic group having 3 to 10 carbon atoms which may have a substituent, or the like.
In the general formula (IV), Y represents an alkylene group having 2 to 6 carbon atoms, and may be, for example, -CH2CH2-、-CH2CH2CH2-、-CH(CH3)CH2-and the like.
From one to anotherFrom the viewpoint of increasing the resolution, it is also preferable that- (Y-O) in the general formula (IV)s-a partial sum- (Y-O)t-the moieties are independently of each other- (C)2H5O)-(C3H6O)9-replacing.
As (b)4) Preferable specific examples of the urethane di (meth) acrylate compound represented by the general formula (IV) include addition reaction products of a (meth) acrylic monomer having a hydroxyl group at the β -position and diisocyanate compounds such as isophorone diisocyanate, 2, 6-toluene diisocyanate, 2, 4-toluene diisocyanate, and 1, 6-hexamethylene diisocyanate, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, and EO-and PO-modified urethane di (meth) acrylate. The EO represents ethylene oxide, and the EO-modified compound has an ethylene oxide-based block structure. Further, PO represents propylene oxide, and the PO-modified compound has a block structure of a propylene oxide group. Examples of the EO-modified urethane di (meth) acrylate include a product name "UA-11" manufactured by Ninghamura chemical industries, Ltd. Further, as the EO or PO modified urethane di (meth) acrylate, for example, a trade name "UA-13" manufactured by Nippon Komura chemical Co., Ltd. These can be used alone in 1 or a combination of 2 or more.
The ethylenically unsaturated bond-containing compound (B) preferably contains (B) from the viewpoint of suppressing generation of aggregates at the time of development of a photosensitive resin layer formed from the photosensitive resin composition5) A tetra (meth) acrylate compound represented by the general formula (XI).
X in the general formula (XI) is an alkylene group having 2 to 6 carbon atoms, and may be, for example, -CH2CH2-、-CH2CH2CH2-、-CH(CH3)CH2-and the like.
As (b)5) Preferable specific examples of the tetra (meth) acrylate compound represented by the general formula (XI) include pentaerythritol tetra (meth) acrylate, pentaerythritol (poly) alkoxy tetra (meth) acrylate and the like.
(B) The compound containing an ethylenically unsaturated bond may contain other than (b)1)～(b5) An addition polymerizable monomer other than the component (b)6) And (3) components.
As (b)6) The following substances may be mentioned as components:
except that (b)3) Tri (meth) acrylates other than the component (a), such as trimethylolpropane tri (meth) acrylate, ethoxylated glycerol tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate, etc.;
except that (b)5) Tetra (meth) acrylates other than the component (a), such as ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and the like; penta (meth) acrylates such as dipentaerythritol penta (meth) acrylate and the like;
Hexa (meth) acrylates such as dipentaerythritol hexa (meth) acrylate, hexa (meth) acrylate obtained by adding ethylene oxide to 6 ends of dipentaerythritol by a total amount of 1 to 24 moles, hexa (meth) acrylate obtained by adding epsilon-caprolactone to 6 ends of dipentaerythritol by a total amount of 1 to 10 moles, and the like;
an acrylate compound having 1 (meth) acryloyl group;
a compound obtained by reacting a polyhydric alcohol with an α, β -unsaturated carboxylic acid;
a compound obtained by reacting a glycidyl group-containing compound with an α, β -unsaturated carboxylic acid; and
phthalic acid-based compounds such as γ -chloro-2-hydroxypropyl- β '- (meth) acryloyloxyethyl-phthalate and β -hydroxyalkyl- β' - (meth) acryloyloxyalkyl-phthalate, and the like.
In the fourth embodiment, the total content of all the ethylenically unsaturated bond-containing compounds (B) in the photosensitive resin composition is preferably in the range of 1 to 70% by mass, more preferably 2 to 60% by mass, and even more preferably 4 to 50% by mass, from the viewpoint of the edge fusion property and the adhesion property of the photosensitive resin laminate.
[ (C) photopolymerization initiator ]
(C) The component (B) is a component which generates a radical capable of initiating polymerization of the component (B) by irradiation with light.
Examples of the component (C) include aromatic ketone compounds, quinone compounds, benzoin ether compounds, benzoin compounds, benzil compounds, hexaarylbiimidazole compounds, and acridine compounds. Among them, from the viewpoint of high resolution and good pore-capping property, 1 or more selected from hexaarylbiimidazole compounds and acridine compounds are preferably used. In addition, from the viewpoint of sensitivity of the photosensitive resin composition, the component (C) preferably contains an acridine compound.
Examples of the hexaarylbiimidazole compound include 2- (o-chlorophenyl) -4, 5-diphenylimidazolyl dimer, 2 ', 5-tris- (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4', 5 '-diphenylimidazolyl dimer, 2, 4-bis- (o-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -diphenylimidazolyl dimer, 2,4, 5-tris- (o-chlorophenyl) -diphenylimidazolyl dimer, 2- (o-chlorophenyl) -bis-4, 5- (3, 4-dimethoxyphenyl) -imidazolyl dimer, 2' -bis- (2-fluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2, 3-difluoromethylphenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2, 4-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2, 5-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2, 6-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2,3, 4-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2,3, 5-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2,3, 6-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 ' -bis- (2,4, 5-trifluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 '-bis- (2,4, 6-trifluorophenyl) -4, 4', 5,5 '-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2' -bis- (2,3,4, 5-tetrafluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 '-bis- (2,3,4, 6-tetrafluorophenyl) -4, 4', 5,5 '-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2' -bis- (2,3,4,5, 6-pentafluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, and the like.
Examples of the acridine compound include:
acridine, 9-phenylacridine, 1, 6-bis (9-acridinyl) hexane, 1, 7-bis (9-acridinyl) heptane, 1, 8-bis (9-acridinyl) octane, 1, 9-bis (9-acridinyl) nonane, 1, 10-bis (9-acridinyl) decane, 1, 11-bis (9-acridinyl) undecane, 1, 12-bis (9-acridinyl) dodecane, and the like.
The content of the component (C) in the photosensitive resin composition of the fourth embodiment is preferably 0.1 to 2% by mass, more preferably 0.2 to 1.8% by mass, still more preferably 0.3 to 1.7% by mass, and particularly preferably 0.4 to 1.6% by mass. When the content of the component (C) is set in such a range, it is preferable from the viewpoint of obtaining good sensitivity and peeling characteristics.
From the viewpoint of improvement in sensitivity and resolution, the (C) component may further contain a sensitizer. Examples of such sensitizers include N-aryl amino acids, organic halogen compounds, and other sensitizers.
Examples of the N-aryl amino acid include:
n-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, and the like;
Examples of the organic halogen compound include:
amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, dibromomethane, tribromomethylphenylsulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1, 1-trichloro-2, 2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds, and the like.
Examples of the other sensitizers include:
quinone compounds such as 2-ethylanthraquinone, octaethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-benzoanthraquinone, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2-methyl-1, 4-naphthoquinone, 2, 3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone;
aromatic ketone compounds such as benzophenone, michelson [4,4 '-bis (dimethylamino) benzophenone ], 4' -bis (diethylamino) benzophenone, and the like;
benzoin ether compounds such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin;
oxime ester compounds such as benzildimethylketal, benzildiethylketal, 1-phenyl-1, 2-propanedione-2-O-benzoyl oxime, and 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime;
And the like.
The content of the sensitizer in the fourth embodiment is preferably 0.01 to 5 mass%, more preferably 0.05 to 3 mass%, and still more preferably 0.1 to 2 mass% from the viewpoints of the sensitivity of the composition and the releasability of the resist cured film.
In the photosensitive resin composition of the fourth embodiment, when an acridine compound and an N-aryl amino acid are used as the component (C) and they are used in combination within the above-described use ratio range, it is preferable from the viewpoint of suppressing the etching rate at the time of forming a conductor pattern and suppressing the difference in the aspect ratio of the wiring width.
[ (D) stabilizer ]
The photosensitive resin composition may contain a stabilizer as desired. In the fourth embodiment, a hindered phenol is preferably used as the stabilizer from the viewpoint of improving the resolution. Generally, hindered phenols are sterically bulky phenols. The photosensitive resin composition contains a compound represented by the following general formula (V) as a hindered phenol:
Figure BDA0003379849860000771
{ formula (II) wherein R51Represents an optional quiltSubstituted, straight chain alkyl, branched alkyl, aryl, cyclohexyl, straight chain alkyl sandwiching a divalent linking group, branched alkyl sandwiching a divalent linking group, cyclohexyl sandwiching a divalent linking group, or aryl sandwiching a divalent linking group, and R 52、R53And R54Each independently represents hydrogen, or an optionally substituted, straight-chain alkyl group, branched-chain alkyl group, aryl group, cyclohexyl group, straight-chain alkyl group sandwiching a divalent linking group, branched-chain alkyl group sandwiching a divalent linking group, cyclohexyl group sandwiching a divalent linking group, or aryl group sandwiching a divalent linking group. }.
The compound represented by the general formula (V) is excellent in terms of improving the resolution of the photosensitive resin composition and suppressing the decrease in sensitivity of the photosensitive resin composition. The compound represented by the general formula (V) does not have 2 or more phenolic hydroxyl groups on 1 aromatic ring, and has a substituent at only one of the two ortho-positions of the phenolic hydroxyl group, and is characterized in that steric hindrance around the phenolic hydroxyl group is controlled. It is considered that the above excellent properties are exhibited by such a structure.
From the viewpoint of improving the resolution of the photosensitive resin composition and the viewpoint of suppressing the decrease in sensitivity of the photosensitive resin composition, the compound represented by the general formula (V) is preferably such that R in the formula (V)51、R52、R53And R54At least 1 of them has an aromatic ring. From the same viewpoint, the hydroxyl group concentration of the hindered phenol is preferably 0.10mol/100g to 0.75mol/100 g. From the same viewpoint, it is preferable that R in the general formula (V) is 51、R52、R53And R54At least 1 of them is a linear or branched alkyl group or an aryl group sandwiching a divalent linking group, and preferable examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group, and preferable examples of the divalent linking group include a thioether group, a substituted or unsubstituted alkylene group, and the aryl group may be substituted with a hydroxyl group or an alkyl group.
From the same viewpoint, the compound represented by the general formula (V) is preferably, for example, a compound represented by the following general formula (VI), a compound represented by the following general formula (VIII), a compound represented by the following general formula (IX), or a compound represented by the following general formula (X):
Figure BDA0003379849860000781
{ formula (II) wherein R55Represents a general formula (VII), and R56、R57And R58Independently of one another, represents hydrogen or the following general formula (VII):
Figure BDA0003379849860000791
[ in the formula, R59And R60Independently of one another, hydrogen or optionally substituted straight-chain alkyl, branched-chain alkyl, aryl, cyclohexyl.]。}、
Figure BDA0003379849860000792
{ formula (II) wherein R61And R64Independently of one another, represents a linear or branched alkyl group, and R62、R63、R65And R66Independently of one another, represent hydrogen or a linear or branched alkyl radical, X1Represents a divalent linking group. H is arranged,
Figure BDA0003379849860000793
{ formula (II) wherein R67、R70And R73Independently of one another, represents a linear or branched alkyl group, and R 68、R69、R71、R72、R74And R75Independently of one another, represents hydrogen or a linear or branched alkyl radical, Y1Represents a trivalent linking group. H is arranged,
Figure BDA0003379849860000801
{ formula (II) wherein R76、R79、R82And R85Independently of one another, represents a linear or branched alkyl group, and R77、R78、R80、R81、R83、R84、R86And R87Independently of one another, represent hydrogen or a linear or branched alkyl radical, Z1Represents a tetravalent linker group. }. X in the above general formula (VIII) is1Examples thereof include a thioether group and a substituted or unsubstituted alkylene group.
From the viewpoint of improving the resolution of the photosensitive resin composition and suppressing the decrease in sensitivity of the photosensitive resin composition, the compound represented by the general formula (V) preferably has a molecular weight of about 130 to about 1000, more preferably has a molecular weight of about 200 to about 800, further preferably has a molecular weight of about 300 to about 500, and most preferably has a molecular weight of about 300 to about 400. In addition, it is preferable to have a specific gravity of about 1.02 to about 1.12 or a melting point of about 155 ℃ or higher (e.g., about 208 ℃ or higher); or, it is poorly soluble in water and is easily soluble in organic solvents such as methanol, acetone, toluene, and the like; or a solid (e.g., powder, crystals, etc.) or liquid when used.
Examples of the compound represented by the general formula (V) include 4,4 '-thiobis (6-tert-butyl-m-cresol), 4' -butylidenebis (3-methyl-6-tert-butylphenol), styrenated phenol (ANTAGE SP manufactured by Kayokoku Kagaku K.K.), tribenzylphenol (TBP manufactured by Kayokoku K.K., phenol having 1 to 3 benzyl groups), and the like. Among these, 4 '-thiobis (6-tert-butyl-m-cresol) and 4, 4' -butylidenebis (3-methyl-6-tert-butylphenol) are preferable from the viewpoint of improving the resolution and the viewpoint of suppressing the decrease in sensitivity of the photosensitive resin composition because the content of the compound represented by the general formula (I) is large.
The proportion of the compound represented by the general formula (V) is 0.001 to 10% by mass relative to the total mass of the photosensitive resin composition. The ratio is 0.001 mass% or more, preferably 0.01 mass% or more, more preferably 0.05 mass% or more, still more preferably 0.1 mass% or more, particularly preferably 0.5 mass% or more, and most preferably 0.7 mass% or more, from the viewpoint of improving the resolution. On the other hand, the ratio is 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, and particularly preferably 1.5% by mass or less, from the viewpoint of reducing sensitivity reduction and improving resolution.
In the fourth embodiment, the hindered phenol may further contain a compound other than the compound represented by the general formula (V). Examples of the compound other than the compound represented by the general formula (V) include 2, 6-di-tert-butyl-4-methylphenol, 2, 5-di-tert-amylhydroquinone, 2, 5-di-tert-butylhydroquinone, 2' -methylenebis (4-methyl-6-tert-butylphenol), bis (2-hydroxy-3-tert-butyl-5-ethylphenyl) methane, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1, 6-hexanediol-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], (a-tert-butyl-4-hydroxyphenyl) propionate), 2, 2-thio-diethylenebis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamamide), diethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate and the like.
In the fourth embodiment, the total content of all hindered phenols in the photosensitive resin composition is preferably 0.001 to 10% by mass relative to the total mass of the photosensitive resin composition.
In the fourth embodiment, the photosensitive resin composition may contain a stabilizer other than hindered phenol. As the stabilizer other than the hindered phenol, it is preferable to contain at least 1 selected from the group consisting of: radical polymerization inhibitors such as p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, 2, 6-di-t-butyl-p-cresol, 2 '-methylenebis (4-methyl-6-t-butylphenol), 2' -methylenebis (4-ethyl-6-t-butylphenol), diphenylnitrosamine, triethylene glycol-bis (3-3-t-butyl-5-methyl-4-hydroxyphenyl propionate), and nitrosophenylhydroxylamine aluminum salt; benzotriazoles such as 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-tolyltriazole, 1- (2-di-N-octylaminomethyl) -benzotriazole, and bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole; carboxybenzotriazoles, for example 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, 6-carboxy-1, 2, 3-benzotriazole, 1- (2-di-n-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole in a molar ratio of 1: 1 mixture, N- (N, N-di-2-ethylhexyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole, and the like; and alkylene oxide compounds having a glycidyl group such as neopentyl glycol diglycidyl ether (for example, Eplight 1500NP manufactured by Kyoeisha chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (for example, Eplight 400E manufactured by Kyoeisha chemical Co., Ltd.), bisphenol A-propylene oxide 2 molar adduct diglycidyl ether (for example, Eplight 3002 manufactured by Kyoeisha chemical Co., Ltd.), hydrogenated bisphenol A diglycidyl ether (for example, Eplight 4000 manufactured by Kyoeisha chemical Co., Ltd.), 1, 6-hexanediol diglycidyl ether (for example, Eplight 1600 manufactured by Kyoeisha chemical Co., Ltd.), and the like.
In the fourth embodiment, the total content of all the stabilizers in the photosensitive resin composition is preferably in the range of 0.001 to 3% by mass, more preferably 0.01 to 1% by mass, and still more preferably 0.05 to 0.7% by mass. The total content of the stabilizer is preferably 0.001 mass% or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably 3 mass% or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.
[ other ingredients ]
The photosensitive resin composition of the fourth embodiment may contain other components in addition to the components (a) to (D) described above. Examples of such other components include leuco dyes, basic dyes, plasticizers, antioxidants, radical polymerization inhibitors, and solvents.
[ leuco dye ]
The leuco dye may be blended in the photosensitive resin composition of the fourth embodiment in order to impart appropriate color developability and excellent peeling characteristics to the resist cured film.
Specific examples of the leuco dye include leuco crystal violet (tris [4- (dimethylamino) phenyl ] methane), 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azabiphthalide, 1, 3-dimethyl-6-diethylaminofluorane, 2-chloro-3-methyl-6-dimethylaminofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, and mixtures thereof, 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-xylenylaminofluoran, 2- (2-chloroanilino) -6-dibutylaminofluoran, 3, 6-dimethoxyfluoran, 3, 6-di-N-butoxyfluoran, 1, 2-benzo-6-diethylaminofluoran, 1, 2-benzo-6-dibutylaminofluoran, 1, 2-benzo-6-ethylideneaminofluoran, 2-methyl-6- (N-p-toluene-N-ethylamino) fluoran, 2- (N-phenyl-N-methylamino) -6- (N-p-toluene-N-ethylamino) fluoran, 2- (3' -trifluoromethylanilino) -6-diethylaminofluoran, 3-chloro-6-cyclohexylaminofluoran, 2-methyl-6-cyclohexylaminofluoran, 3-methoxy-4-dodecyloxystyrenylquinoline, and the like. Among them, leuco crystal violet is preferable.
The content of the leuco dye in the photosensitive resin composition of the fourth embodiment is preferably 0.6 to 1.6% by mass, more preferably 0.7 to 1.2% by mass. By setting the use ratio of the leuco dye to this range, good color developability and good releasability can be achieved.
[ basic dye ]
Examples of the basic dye include basic green 1[ CAS number (the same applies below): 633-03-4] (e.g., Aizen Diamond Green GH, trade name, manufactured by Baotou chemical industries, Ltd.), Malachite Green oxalate [2437-29-8] (e.g., Aizen Malachite Green, trade name, manufactured by Baotou chemical industries, Ltd.), brilliant Green [633-03-4], fuchsin [632-99-5], methyl violet [603-47-4], methyl violet 2B [8004-87-3], crystal violet [548-62-9], methyl Green [82-94-0], Victoria Blue B [2580-56-5], basic Blue 7[2390-60-5] (e.g., Aizen Victoria Pure Blue BOH, trade name, manufactured by Baoto chemical industries, Ltd.), rhodamine B [81-88-9] (Hadamia, Rhodamine 6G [989-38-8], basic yellow 2[2465-27-2], diamond green and the like. Among them, 1 or more selected from basic green 1, malachite green oxalate, basic blue 7, and diamond green are preferable, and basic green 1 is particularly preferable from the viewpoint of hue stability and exposure contrast.
The content of the basic dye in the photosensitive resin composition of the fourth embodiment is preferably in the range of 0.001 to 3% by mass, more preferably in the range of 0.01 to 2% by mass, and still more preferably in the range of 0.01 to 1.2% by mass. By adopting the use ratio in this range, both good color rendering properties and high sensitivity can be achieved.
[ solvent ]
The photosensitive resin composition of the fourth embodiment may be a mixture of the above-mentioned components (a) to (C) and optionally other components, or may be used in the form of a photosensitive resin composition preparation solution prepared by adding an appropriate solvent to these components.
Examples of the solvent used herein include ketone compounds such as Methyl Ethyl Ketone (MEK); alcohols such as ethanol, ethanol and isopropanol; and the like.
The solvent is preferably used in such a proportion that the viscosity of the photosensitive resin composition preparation liquid at 25 ℃ is 500 to 4000mPa · s.
< photosensitive element >
In the fourth embodiment, the photosensitive element is a laminate (photosensitive resin laminate) in which a photosensitive resin layer formed of the photosensitive resin composition is laminated on a support. If necessary, the photosensitive resin layer may have a protective layer on the surface thereof opposite to the support.
[ support ]
The support is preferably a transparent substrate that transmits light emitted from the exposure light source. Examples of such a support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, stretched films may also be used as needed.
The haze of the support is preferably 5 or less.
The support is advantageous in terms of image formability and economy when the thickness is small, but needs to maintain strength. In view of both, a support of 10 μm to 30 μm may be preferably used.
[ photosensitive resin layer ]
When the photosensitive resin composition used for forming the photosensitive resin layer contains a solvent, the solvent may remain in the photosensitive resin layer, but it is preferable that the solvent is removed.
The thickness of the photosensitive resin layer is preferably 5 to 100 μm, more preferably 7 to 60 μm. The thinner the thickness, the higher the resolution, and the thicker the thickness, the higher the film strength. Therefore, the thickness of the composition layer can be appropriately adjusted within the above range according to the use.
[ protective layer ]
The important characteristic of the protective layer is that the adhesion force with the photosensitive resin layer is sufficiently smaller than the adhesion force between the support and the photosensitive resin layer, and the protective layer can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film, or the like can be preferably used, and for example, a film excellent in peelability disclosed in jp 59-202457 a can be used.
The thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.
[ method for producing photosensitive element ]
The photosensitive element can be produced by sequentially laminating a support, a photosensitive resin layer, and a protective layer as needed. As a method for laminating the support, the photosensitive resin layer, and the protective layer, a known method can be used.
For example, a photosensitive resin composition is prepared as the photosensitive resin composition preparation liquid, and first, a photosensitive resin layer formed of the photosensitive resin composition is formed on a support by coating the photosensitive resin composition on the support using a bar coater or a roll coater and drying the coating. Next, a protective layer is laminated on the formed photosensitive resin layer as necessary, whereby a photosensitive element can be manufactured.
< method for forming resist Pattern >
A resist pattern can be formed on a substrate using the photosensitive element as described above.
The method for forming a resist pattern preferably includes the following steps in this order:
a laminating step of laminating a photosensitive resin layer of the photosensitive element on the conductor substrate;
an exposure step of exposing the laminated photosensitive resin layer; and
and a developing step of developing the exposed photosensitive resin layer.
In the method for forming a resist pattern according to the fourth embodiment, first, in the laminating step, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive element has a protective layer, the photosensitive resin layer is heated and pressed against the surface of the substrate using a laminator to laminate after the protective layer is peeled off.
As the substrate, a metal plate or an insulating substrate having a metal coating film is used. Examples of the material of the metal include copper, stainless steel (SUS), glass, and Indium Tin Oxide (ITO). These substrates may also have through holes for handling multilayer substrates.
Here, the photosensitive resin layer may be laminated only on one surface of the substrate surface, or may be laminated on both surfaces of the substrate as necessary. The heating temperature in this case is preferably 40 to 160 ℃. From the viewpoint of further improving the adhesion of the obtained resist pattern to the substrate, the thermocompression bonding is preferably performed 2 or more times. When the pressure bonding is performed 2 or more times, a two-stage laminator having two or more rollers may be used, or the pressure bonding may be performed by passing the laminate of the substrate and the photosensitive resin layer through the rollers several times.
In the laminating step, the photosensitive resin layer of the photosensitive element may be laminated on the conductor substrate with the wetting agent interposed therebetween. This is a preferable lamination method from the viewpoint of improving the following property and yield. As the wetting agent, 1 or more selected from pure water, deionized water and electrolyzed water, and a copper chelating agent (for example, 1 or more selected from the group consisting of an imidazole compound, a triazole compound, a pyridine compound and a pyrazole compound) are preferably contained.
Next, in the exposure step, the photosensitive resin layer is exposed by using an exposure machine. The exposure may be performed through the support without peeling the support, or may be performed after peeling the support as necessary.
By performing this exposure in a pattern, a resist film (resist pattern) having a desired pattern can be obtained after a developing step described later. The pattern-like exposure can be performed by either a method of exposing light through a photomask or a maskless exposure. When exposure is performed through a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time. The exposure amount may be measured using a light meter.
In the maskless exposure, exposure is performed on a substrate by a direct writing apparatus without using a photomask. As the light source, a semiconductor laser having a wavelength of 350nm to 410nm, an ultra-high pressure mercury lamp, or the like is used. In the maskless exposure, a drawing pattern is controlled by a computer, and the exposure amount is determined by the illuminance of an exposure light source and the moving speed of a substrate.
Next, in the developing step, the exposed photosensitive resin layer is developed. For example, an unexposed portion of the photosensitive resin layer is removed with a developer. When the support is provided on the photosensitive resin layer after exposure, it is preferably removed and then subjected to a developing step.
In the developing step, the unexposed portion is developed and removed using a developer composed of an aqueous alkali solution, thereby obtaining a resist image. As the aqueous alkali solution, for example, Na is preferably used2CO3、K2CO3And the like. The alkali aqueous solution is selected according to the characteristics of the photosensitive resin layer, and preferably 0.2 to 2 mass% of Na is used2CO3An aqueous solution. The aqueous alkali solution may contain a surfactant, a defoaming agent, a small amount of an organic solvent for promoting development, and the like.
The temperature of the developer in the developing step is preferably kept constant within a range of 20 ℃ to 40 ℃.
The resist pattern is obtained by the above-described steps. In some cases, the heating step may be further performed at 100 to 300 ℃. The heating step is preferably performed from the viewpoint of further improving the chemical resistance. The heating may be performed by a heating furnace using a suitable method such as hot air, infrared rays, or far infrared rays.
< method for forming circuit board >
The method for forming a circuit board according to the fourth embodiment preferably includes the following steps in this order:
a laminating step of laminating a photosensitive resin layer of the photosensitive element on the conductor substrate;
an exposure step of exposing the laminated photosensitive resin layer;
a developing step of developing the exposed photosensitive resin layer;
a conductor pattern forming step of etching or plating the conductor substrate on which the resist pattern is formed by development; and
and a stripping step of stripping the resist pattern.
In the conductor pattern forming step, a conductor pattern may be formed on the substrate having the resist pattern formed thereon by a known etching method or plating method on the surface (e.g., copper surface) of the substrate exposed in the developing step.
In the stripping step, the substrate on which the conductor pattern is formed is brought into contact with an appropriate stripping liquid to strip and remove the resist pattern. Through this process, a desired circuit board is obtained.
The stripping liquid used in the stripping step is preferably an aqueous alkali solution. As the aqueous alkali solution, for example, a 2 to 5 mass% aqueous NaOH solution or an aqueous KOH solution is preferably used. A small amount of a water-soluble solvent such as alcohol may be added to the stripping solution. The temperature of the stripping solution in the stripping step is preferably 40 to 70 ℃.
The photosensitive resin composition, photosensitive element, resist pattern formation method, and circuit board production method of the fourth embodiment can be used suitably for production of, for example, printed circuit boards, lead frames, substrates having uneven patterns, semiconductor packages, and the like.
The measurement methods of the various parameters described above are, unless otherwise specified, measured according to the measurement methods in the examples described below.
Examples
< example and comparative example according to the first embodiment >
Hereinafter, the photosensitive resin composition of the first embodiment will be specifically described as an example.
(1) Measurement of physical Property values of raw materials
< determination of weight average molecular weight >
The weight average molecular weight of the polymer was determined as a polystyrene equivalent using 4-column tandem Gel Permeation Chromatography (GPC) (pumps: Gulliver, PU-1580 type, columns: Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) manufactured by Showa Denko K.K., tetrahydrofuran as a mobile phase solvent, and a calibration curve obtained using a polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.) as a polystyrene standard.
< acid equivalent >
In the present specification, the acid equivalent means the mass (g) of the polymer having 1 equivalent of carboxyl group in the molecule. The acid equivalent was measured by a potentiometric titration method using a 0.1mol/L aqueous sodium hydroxide solution using a Hei Marsh automatic titrator (COM-555) manufactured by Hei Marsh industries, Ltd.
(2) Method for producing sample for evaluation and analysis
< production of photosensitive element >
Each of the components shown in table 1 and the following components were mixed, and Methyl Ethyl Ketone (MEK) was further added to prepare a photosensitive resin composition having a solid content of 53 mass%.
As a coloring matter, 0.04 parts by mass of diamond green;
0.6 part by mass of leuco crystal violet as a leuco dye;
0.7 part by mass of tribromomethylphenyl sulfone as a halogen compound;
2 parts by mass of p-toluenesulfonamide as a plasticizer;
as the benzotriazoles, carboxybenzotriazole 0.05 parts by mass;
as the benzotriazole, 0.15 part by mass of 1- (2-di-n-octylaminomethyl) -benzotriazole;
as an antioxidant, 0.05 part by mass of hydrogenated bisphenol a diglycidyl ether (kyo chemical, Epolight 4000); and
0.004 part by mass of tris (nitrosophenylhydroxylamine) aluminum as a radical polymerization inhibitor.
The numbers in the columns of the respective ingredients in table 1 are amounts (parts by mass) of the respective ingredients for preparation of the compositions.
The obtained photosensitive resin composition was uniformly applied to a polyethylene terephthalate film (R310, haze value 2.1%, manufactured by Mitsubishi resin corporation) having a thickness of 16 μm as a support by using a bar coater, and then, the resultant was dried by heating in a dryer adjusted to 95 ℃ for 2.5 minutes to form a photosensitive resin composition layer having a thickness of 25 μm on the support.
Next, a polyethylene film (GF-18 manufactured by tamapol co., ltd.) having a thickness of 19 μm as a protective layer was attached to the surface of the photosensitive resin composition layer opposite to the support, to obtain a photosensitive element.
< substrate used in evaluation >
As a substrate for evaluation of the hole-covering ability, a substrate was used in which 1008 through holes having a diameter of 6mm were formed in a 1.6mm thick copper-clad laminate substrate on which 35 μm thick copper foil was laminated;
as the substrate for evaluation other than the pinhole characteristic, a copper-clad laminate substrate having a thickness of 0.4mm, on which a copper foil having a thickness of 18 μm was laminated, was used.
The substrate for evaluation of the hole-covering property was subjected to surface conditioning by a surface treatment using a jet-type sand-grinding grinder and then subjected to evaluation.
The substrate for evaluation other than the hole-capping property was subjected to surface treatment with a soft etchant (CPE-900, manufactured by Mitsubishi chemical corporation) and surface treatment with 10 mass% H2SO4The surface of the aqueous solution was cleaned to adjust the surface and evaluated.
< lamination >
The polyethylene films of the photosensitive elements obtained in examples and comparative examples were peeled off from the surface-conditioned substrate, and laminated in a hot roll laminator (AL-70, manufactured by asahi chemicals) at a roll temperature of 105 ℃, an air pressure of 0.35MPa, and a lamination speed of 1.5 m/min.
< Exposure >
Exposure was performed by a direct write exposure method using a direct write exposure apparatus (manufactured by Orbotech ltd., paramon Ultra 200, main wavelength 355 nm).
The exposure pattern is described later in the items of the respective evaluation items.
< development >
After the support was peeled from the exposed photosensitive resin composition layer, 1 mass% Na at 30 ℃ was sprayed for a time 2 times as long as the minimum development time using an alkali developing machine (FUJI KIKOU co., ltd2CO3And (3) dissolving and removing the unexposed part of the photosensitive resin composition layer by using an aqueous solution. After the development, the substrate was cleaned with pure water for 1.5 times the development time, subjected to water removal treatment with an air knife, and then dried with warm air to obtain a substrate having a cured film for evaluation.
The minimum development time is a minimum time required until the unexposed portion of the photosensitive resin composition layer is completely dissolved and removed.
< evaluation of sensitivity >
For the evaluation of sensitivity, a laminated substrate after 15 minutes had passed after the above-mentioned < lamination > was used.
The laminated substrate was developed by the method described in < development > after directly drawing and exposing a mask pattern of 10 lines having a line/space of 40 μm/40 μm. The resist top width of the obtained resist pattern was measured by an optical microscope, and the sensitivity was evaluated according to the following criteria.
The exposure dose for the resist top width to 39.0 μm was 28mJ or less: sensitivity ". smallcircle. (good)"
The exposure dose for the resist top width to 39.0 μm exceeds 28 mJ: sensitivity "X (poor)"
Here, the measurement position of the resist line is a position of the 5 th line from the end among the 10 lines and about 5mm from the end in the longitudinal direction, and an average value of 3 measurements is used as the measurement value. The line width of the pattern at the end and the center portion is different due to the influence of the diffusion of the developer and the cleaning water, and the resist line at the end portion tends to be thin.
The exposure dose in the following evaluation items was the exposure dose at which the resist top width reached 39.0 μm for a mask pattern having a line/space of 40 μm/40 μm as described in the above < evaluation of sensitivity >.
< evaluation of resolution >
For the evaluation of the resolution, a laminated substrate after 15 minutes had passed after the above-mentioned < lamination > was used.
The laminated substrate was developed by the method described in < development > after directly drawing and exposing patterns of various sizes of line/space 1/1.
The minimum pattern width formed was observed with an optical microscope for the obtained pattern, and the resolution was evaluated according to the following criteria.
A minimum pattern width of 20 μm or less: resolution ". smallcircle (good)"
A minimum pattern width exceeding 20 μm and being 24 μm or less: resolution "delta (can)"
Case where the minimum pattern width exceeds 24 μm: resolution "X (poor)"
< adhesion >
For evaluation of adhesion, a laminated substrate after 15 minutes had passed after the above-mentioned < lamination > was used.
The laminated substrate was developed by the method described in < development > after directly drawing and exposing the pattern of the individual lines of various sizes.
The obtained pattern was observed with an optical microscope, and the adhesion was evaluated according to the following criteria.
The minimum pattern width normally formed is 18 μm or less: seal property ` good ` "
The minimum pattern width normally formed exceeds 18 μm and is 22 μm or less: adhesion "Delta (may)"
The minimum pattern width normally formed exceeds 22 μm: adhesion "X (poor)"
Here, the case where the line pattern is not normally formed means a case where the line pattern collapses, a case where the line pattern meanders, or a case where the line pattern is not present on the substrate.
< porosity >
The evaluation of the hole-covering property was carried out by observing the laminated substrate after the above < lamination > obtained using the substrate having the through-hole.
The number of holes in which the photosensitive resin composition layer (cap film) formed on the through-hole was broken was measured, and the ratio to all the holes (cap film breakage ratio) was calculated and evaluated according to the following criteria.
Case where the lid hole film breakage rate is less than 0.1%: very good property of covering hole "
The lid hole film breakage rate is 0.1% or more and less than 2%: good hole-covering property "
Case where the lid hole film breakage rate is 2% or more: (bad) porosity of X "
< etching speed (wiring bottom width) >)
For the evaluation of the etching rate (width of bottom of wiring), a laminated substrate after 15 minutes from the above-mentioned < lamination > was used.
For the laminated substrate, a pattern having 10 lines with a line/space of 50 μm/30 μm was directly drawn and exposed. After 15 minutes from the exposure, the support was peeled from the photosensitive resin composition layer, and 1 mass% Na at 30 ℃ was sprayed for a time 2 times as long as the minimum development time using an alkali developing machine (FUJI KIKOU co., ltd 2CO3And (3) dissolving and removing the unexposed part of the photosensitive resin composition layer by using an aqueous solution. After the development, washing was performed with pure water for a time 1.5 times as long as the development time.
Then, the substrate having the line/space pattern after water washing was introduced into a copper chloride etching apparatus (NLE-2000, manufactured by tokyo chemical company, inc.) without drying so that the line/space orientation of the substrate was orthogonal to the transport direction (MD), and etching was performed at a line speed of 2.0 m/min for 55 seconds under conditions of a hydrochloric acid concentration of 3.2 mol/L, a copper chloride concentration of 2.0 mol/L, an etching spray pressure of 0.2MPa, and an etching solution temperature of 50 ℃.
After the etching, the cured film on the substrate was peeled and removed at 50 ℃ using a NaOH aqueous solution having a concentration of 3.0 mass% as a peeling liquid, and the bottom width of the wiring pattern in the MD direction of the copper wire thus obtained was measured by an optical microscope.
Here, the measurement position of the line of the wiring pattern is set to a position of 5 th line from the end of 10 lines and about 5mm from the end in the longitudinal direction, and an average value of 3 measurements is used as the measurement value. Since the resist is affected differently by the diffusion of the developer and the cleaning water at the edge and the center of the pattern, the line width of the final wiring line is different, and the wiring line width at the edge tends to be narrow.
< aspect ratio of wiring width >
For evaluation of the difference in the width of the wiring between the two sides, a laminate substrate obtained after 15 minutes had passed after the above-mentioned < lamination > was used.
For the laminated substrate, a pattern of 10 lines with a line/space of 50 μm/30 μm was directly subjected to drawing exposure in an exposure pattern arranged in a tile shape in the MD direction and the TD direction.
After 15 minutes from the exposure, the support was peeled from the photosensitive resin composition layer, and 1 mass% Na at 30 ℃ was sprayed for a time 2 times as long as the minimum development time using an alkali developing machine (FUJI KIKOU co., ltd2CO3And (3) dissolving and removing the unexposed part of the photosensitive resin composition layer by using an aqueous solution. After the development, washing was performed with pure water for a time 1.5 times as long as the development time.
Next, the substrate having the line/space pattern after water washing was introduced into a copper chloride vacuum etching apparatus (FUJI KIKOU co., ltd. manufacture, inlet width 750mm, groove length 2.6m) without drying so that the line/space orientation of the substrate was orthogonal to the transport direction (MD), and 71 second etching was performed at a linear velocity of 2.2 m/min under conditions of 14 lines in the MD direction of the etching solution pipe (pipe interval about 18cm), 14 lines in the TD direction per 1 number of spray nozzles in the pipe (slit nozzle, spray direction parallel to the TD direction, nozzle interval about 14cm, distance from the substrate about 5cm), no vibration, 2.85 mol/L of hydrochloric acid concentration, 2.0 mol/L of copper chloride concentration, 0.3MPa of etching spray pressure, 0.15MPa of vacuum pressure, and 48 ℃ of etching solution temperature.
After the etching, the cured film on the substrate was peeled and removed at 50 ℃ using a NaOH aqueous solution having a concentration of 3.0 mass% as a peeling liquid to obtain 2 sets of line patterns of copper in the MD direction and the TD direction, and the bottom width was measured by an optical microscope.
Here, the measurement position of the line of the wiring pattern is set to a position of 5 th line from the end of 10 lines and about 5mm from the end in the longitudinal direction, and an average value of the measurement values of 3 times is used as the measurement value. Since the resist is affected differently by the diffusion of developer and cleaning water at the end and the center of the pattern, the line width of the final wiring line is different, and the wiring line width at the end tends to be narrow.
The vertical and horizontal differences in the wiring widths were calculated by the following numerical expressions and evaluated according to the following criteria.
Transverse and longitudinal difference (mum) of wiring width TD-MD
The difference in the vertical and horizontal widths of the wiring is 1 μm or less: width of wiring bottom length and width- "
The aspect ratio of the wiring width is more than 1 μm and 2 μm or less: wire bottom width longitudinal and lateral difference ". smallcircle (good)"
The aspect ratio of the wiring width is more than 2 μm and 4 μm or less: width longitudinal and transverse difference of wiring bottom delta (can) "
The aspect ratio of the wiring width exceeds 4 μm: longitudinal and transverse difference of width of wiring bottom x (bad) "
Examples 1 to 23 and comparative examples 1 to 8
The compositions of the photosensitive resin compositions used in examples and comparative examples are shown in Table 1,
the details of the component names shown in table 1 are shown in table 2. The blending amounts of the respective components in table 1 are all parts by mass in terms of solid content.
The results of the evaluations using the respective compositions are shown in table 1.
Figure BDA0003379849860000951
TABLE 2 details of the ingredients (1 st of 2 sheets in total)
Figure BDA0003379849860000961
Figure BDA0003379849860000971
(incomplete table 2)
TABLE 2 composition details 2 nd sheet of 2 sheets
Figure BDA0003379849860000972
< example and comparative example according to the second embodiment >
Hereinafter, the photosensitive resin composition of the second embodiment will be specifically described as an example.
(1) Measurement of physical Property values of raw materials
< acid equivalent >
The acid equivalent means the mass of the alkali-soluble polymer having 1 equivalent of carboxyl group therein. The acid equivalent was measured by a potentiometric titration method using an automatic titrator (e.g., a flat methane automatic titrator (COM-555) manufactured by flatmethane industries co., ltd.) using a 0.1mol/L aqueous solution of sodium hydroxide.
< determination of weight average molecular weight >
The weight average molecular weight of the polymer was determined as a polystyrene equivalent using 4-column tandem Gel Permeation Chromatography (GPC) (pumps: Gulliver, PU-1580 type, columns: Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) manufactured by Showa Denko K.K., tetrahydrofuran as a mobile phase solvent, and a calibration curve obtained using a polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.) as a polystyrene standard.
(2) Method for producing sample for evaluation
< production of photosensitive element >
Each of the components shown in table 3 was mixed, and Methyl Ethyl Ketone (MEK) was further added to prepare a photosensitive resin composition having a solid content concentration of 55 mass%.
The obtained photosensitive resin composition was uniformly applied to a polyethylene terephthalate film (GR-16, manufactured by DuPont film Co., Ltd.) having a thickness of 16 μm as a support by using a bar coater, and then heated and dried in a dryer adjusted to 95 ℃ for 4 minutes to form a photosensitive resin layer having a thickness of 33 μm on the support.
Next, a polyethylene film (GF-18 manufactured by tamapol co., ltd.) having a thickness of 19 μm as a protective layer was attached to the surface of the photosensitive resin layer opposite to the support, thereby obtaining a photosensitive element.
< substrate used in evaluation >
As the substrate for evaluation, a substrate obtained by surface conditioning the surface of a 1.6mm thick copper-clad laminate laminated with a 35 μm rolled copper foil by wet polishing with a polishing roll was used. The polishing was performed by 2 passes using a saki (registered trademark) HD #600 manufactured by 3M company.
< lamination >
The polyethylene films of the photosensitive elements obtained in examples and comparative examples were peeled off from the substrate whose surface had been adjusted and preheated to 60 ℃ and laminated by a hot roll laminator (AL-70, manufactured by asahi chemical company) at a roll temperature of 105 ℃, an air pressure of 0.35MPa, and a lamination speed of 1.5 m/min.
< Exposure >
Using a direct writing exposure machine (Hitachi Via Mechanics Co., Ltd., manufactured by Ltd., DE-1DH, light source: GaN blue-violet diode, dominant wavelength 405. + -.5 nm), a Stouffer 41-level stepwise exposure table or a prescribed mask pattern for DI exposure was used, and at an illuminance of 80mW/cm2Under the conditions of (1) and (2) to an exposure amount equivalent to 14 steps obtained in the Stouffer 41-step exposure table.
< development >
After the support was peeled from the exposed photosensitive resin layer, 1 mass% Na at 30 ℃ was sprayed for a time 2 times as long as the minimum development time using an alkali developing machine (FUJI KIKOU co., ltd2CO3And (4) dissolving and removing the unexposed part of the photosensitive resin layer by using the aqueous solution. After the development, the substrate was washed with pure water for a time 1.5 times as long as the development time, subjected to water removal treatment with an air knife, and then dried with warm air to obtain a substrate having a cured film for evaluation.
The minimum development time is a minimum time required until the unexposed portion of the photosensitive resin layer is completely dissolved and removed.
< etching >
The copper foil of the portion of the copper-clad laminate not covered with the resist pattern was dissolved and removed by spraying a copper chloride etching solution (copper chloride concentration: 250g/L, HCl concentration: 3mol/L) at 50 ℃ for 60 seconds using a copper chloride etching apparatus (manufactured by tokyo chemical co., ltd.) for the evaluation substrate on which the resist pattern was formed by development.
< peeling >
The cured resist was peeled off from the evaluation substrate after etching by spraying a 3 mass% aqueous solution of sodium hydroxide heated to 50 ℃.
(3) Evaluation method
(i) Development aggregation test
The photopolymerizable resin laminate was 50 μm thick and 0.6m in area2The photosensitive layer (resist) of (2) was dissolved in 200ml of 1 mass% Na2CO3The aqueous solution was sprayed at a spray pressure of 0.1MPa for 3 hours by using a circulating spray apparatus. Then, the developer was left for 1 day, and generation of aggregates was observed. When the aggregates were produced in large quantities, powders or oils were observed at the bottom and side of the spray device. In addition, the aggregate may float in the developer. The composition having a good developer aggregating ability does not generate such aggregates at all, or even generates a trace amount of aggregates, and can be easily washed away by water washing. The generation state of aggregates was visually observed, and the aggregates were classified as follows.
Excellent (remarkably good): no aggregates were produced at all.
O (good): no aggregates were present at the bottom or side of the spraying device, and a very small amount of aggregates that could be visually observed floating in the developer were observed, but were simply washed away during the water washing.
Δ (can): aggregates float in the developer and a part of the bottom or side of the spraying device. Even with water, the entire aggregate was not washed off.
X (bad): aggregates were observed in the entire spraying device and floated in the developer. Even with water washing, all the aggregates could not be washed away, and most of them remained.
(ii) Sensitivity test
The photosensitive elements obtained in examples and comparative examples were used in the above-described mannerThe lamination and exposure were carried out, and the exposure amount (mJ/cm) equivalent to 14 in the Stouffer41 stage-wise exposure table was investigated based on each exposure amount and the number of stages remaining after development214/41ST exposure amount) according to the following criteria.
Sensitivity "good" (good): 14/41ST exposure of 25mJ/cm2The following cases
Sensitivity "x" (poor): 14/41ST exposure amount exceeding 25mJ/cm2In the case of
(iii) Resolution test
Using the photosensitive elements obtained in each of examples and comparative examples, lamination was performed according to the above method, and then, after 15 minutes had elapsed, using the thus-obtained sample, line/space was set to 1/1, and further, direct drawing exposure was performed according to the above method. Subsequently, development was performed in the same manner as described above.
Further, the minimum mask line width in which the cured resist line is normally formed was examined and evaluated according to the following criteria.
Resolution "good" (good): the minimum line width is less than 25 μm
Resolution "Δ" (can): minimum line width of 25 μm or more and less than 30 μm
Resolution "x" (poor): minimum line width of 30 μm or more
(iv) Adhesion test
After the photosensitive elements obtained in examples and comparative examples were laminated by the above method, direct drawing exposure was performed by the above method using the samples obtained after 15 minutes. Subsequently, development was performed in the same manner as described above.
Further, assuming that the line/space is X/200, the minimum mask line width that is normally formed is examined as X, and evaluated according to the following criteria.
Good adhesion (good): the minimum line width is less than 25 μm
Adhesion ". DELTA." (possible): minimum line width of 25 μm or more and less than 30 μm
Adhesion "×" (failure): minimum line width of 30 μm or more
Examples 1 to 6 and comparative examples 1 to 5
The compositions of the photosensitive resin compositions used in examples and comparative examples are shown in table 3, and the details of the component names in table 3 are shown in table 4. The blending amounts of the respective components in table 4 are all parts by mass in terms of solid content.
The results of the evaluation using each composition are also shown in table 4.
Figure BDA0003379849860001021
TABLE 4 details of the ingredients
Figure BDA0003379849860001031
< example and comparative example according to the third embodiment >
The photosensitive resin composition of the third embodiment is specifically described below in the form of examples.
The measurement of the physical property values of the polymer and the monomer, and the production methods of the samples for evaluation in examples and comparative examples will be described, and the evaluation method of the obtained samples and the evaluation results thereof will be shown.
(1) Measurement or calculation of physical property values
< measurement of weight-average molecular weight or number-average molecular weight of Polymer >
The weight average molecular weight or number average molecular weight of the polymer was determined as a polystyrene equivalent value by 4-series Gel Permeation Chromatography (GPC) (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) manufactured by Showa Denko K.K., and a mobile phase solvent: tetrahydrofuran, using a standard curve obtained from a polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.) manufactured by Japan.
Further, the degree of dispersion of the polymer was calculated as the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).
< acid equivalent >
In the present specification, the acid equivalent means the mass (g) of the polymer having 1 equivalent of carboxyl group in the molecule. The acid equivalent was measured by a potentiometric titration method using a 0.1mol/L aqueous sodium hydroxide solution using a Hei Marsh automatic titrator (COM-555) manufactured by Hei Marsh industries, Ltd.
(2) Method for producing sample for evaluation
Evaluation samples of examples 1 to 12 and comparative examples 1 to 5 were prepared as follows.
< production of photosensitive resin laminate >
The components shown in the following table 5 or 6 (wherein the numbers of the respective components indicate the blending amount (parts by mass) as a solid component) and a solvent were sufficiently stirred and mixed to obtain a photosensitive resin composition preparation liquid. The names of the components shown in tables 5 and 6 by abbreviations are shown in table 7 below. A polyethylene terephthalate film (R310-16B, manufactured by Mitsubishi resin corporation) having a thickness of 16 μm was used as a support film, and the prepared liquid was uniformly applied to the surface thereof by a bar coater and dried in a drier at 95 ℃ for 3 minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 30 μm.
Next, a 19 μm-thick polyethylene film (GF-818, manufactured by tamapol co., ltd.) was attached as a protective layer to the surface of the photosensitive resin composition layer on the side on which the polyethylene terephthalate film was not laminated, to obtain a photosensitive resin laminate.
< substrate surface finish >
A copper-clad laminate having a thickness of 0.4mm and a 35 μm rolled copper foil laminated thereon was subjected to spray-sanding polishing at a spray pressure of 0.2MPa using an abrasive (サクランダム R (registered trademark #220), manufactured by ltd, Japan Carlit co.
< lamination >
The photosensitive resin laminate was laminated on a copper-clad laminate whose surface was adjusted and preheated to 60 ℃ while peeling the polyethylene film of the photosensitive resin laminate, using a hot roll laminator (manufactured by Asahi Kasei corporation, AL-700) at a roll temperature of 105 ℃ to obtain a test piece. The air pressure was set to 0.35MPa, and the lamination speed was set to 1.5 m/min.
< Exposure >
With a direct drawing type exposure apparatus (Via Mechanics Co., Ltd., DE-1DH, dominant wavelength 405nm) at 15mJ/cm2The exposure is performed with the exposure amount of (1).
< development >
After the polyethylene terephthalate film was peeled from the photosensitive resin laminate, 1 mass% Na at 30 ℃ was sprayed at a developing spray pressure of 0.15MPa using a full cone type nozzle using a developing apparatus manufactured by FUJI KIKOU co2CO3The aqueous solution is sprayed for a predetermined time to develop the photosensitive resin layer, and unexposed portions of the photosensitive resin layer are dissolved and removed. At this time, the minimum time required for the photosensitive resin layer of the unexposed portion to be completely dissolved was measured as the minimum development time, and development was performed in a time 2 times the minimum development time to produce a resist pattern. In this case, the treatment in the water washing step was performed with a flat nozzle under a water washing spray pressure of 0.15MPa for the same time as in the developing step.
(3) Method for evaluating sample
< porosity >
A0.6 mm thick double-sided copper-clad laminate having a through-hole of 2.0mm in width by 15mm in length was subjected to surface treatment with a jet rinsing (jet wiping) type grinder. The lamination was carried out on both sides by the method described in < lamination > above, and the entire sides were exposed with a direct drawing type exposure apparatus (Via Mechanics co., ltd., DE-1DH, dominant wavelength 405 nm). When development was performed by the method described in < development >, the number of broken lid holes was measured, the breakage rate with respect to all lid holes was calculated, and the rating was made according to the following criteria.
Very good (best): the film breakage rate after development was 2% or less.
Very good: the film breakage rate after development exceeded 2% and was 4% or less.
O (good): the film breakage rate after development exceeds 4% and is 10% or less.
X (bad): the film breakage rate after development exceeded 10%.
< contact Angle (suppression of Water remaining short-Circuit trouble) >
In the evaluation of the contact angle (suppression of water remaining short-circuit failure), after lamination was performed by the method described in the above < lamination >, development of the entire surface was performed by the method described in the above < exposure >, and then development was performed by the method described in the above < development >.
After development, the sample is subjected to contact angle measurement within 30 minutes.
Contact Angle measurement according to JIS R3257 static drop method, using Nic company optical microscope contact Angle meter "LSE-B100", at 23 degrees C, humidity 50 RH% environment in the cured film of 0.5 u L pure water drop, the contact angle measurement, using 120 seconds after the value, according to the following standard classification. A large contact angle value indicates that the cured resist has high hydrophobicity and can suppress a water-remaining short circuit failure.
Very good: the contact angle is more than 35 degrees.
O (good): the contact angle is 30 DEG or more and less than 35 deg.
Δ (allowed): the contact angle is 25 DEG or more and less than 30 deg.
X (bad): the contact angle is less than 25 deg.
(4) Evaluation results
The evaluation results of examples 1 to 12 are shown in Table 5 below, and the evaluation results of comparative examples 1 to 5 are shown in Table 6 below.
Figure BDA0003379849860001071
Figure BDA0003379849860001081
TABLE 7
Figure BDA0003379849860001091
< example and comparative example according to the fourth embodiment >
The photosensitive resin composition of the fourth embodiment is specifically described below in the form of examples.
(1) Measurement of physical Property values of raw materials
< determination of weight average molecular weight >
The weight average molecular weight of the polymer was determined as a polystyrene equivalent using 4-column tandem Gel Permeation Chromatography (GPC) (pumps: Gulliver, PU-1580 type, columns: Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) manufactured by Showa Denko K.K., tetrahydrofuran as a mobile phase solvent, and a calibration curve obtained using a polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.) as a polystyrene standard.
< acid equivalent >
In the present specification, the acid equivalent means the mass (g) of the polymer having 1 equivalent of carboxyl group in the molecule. The acid equivalent was measured by a potentiometric titration method using a 0.1mol/L aqueous sodium hydroxide solution using a Hei Marsh automatic titrator (COM-555) manufactured by Hei Marsh industries, Ltd.
(2) Method for producing sample for evaluation and analysis
< production of photosensitive element >
Each of the components shown in table 8 was mixed, and Methyl Ethyl Ketone (MEK) was further added to prepare a photosensitive resin composition having a solid content concentration of 56 mass%. The numbers in the columns of the respective ingredients in table 8 are the amounts (parts by mass) of the respective ingredients for preparation of the compositions.
The obtained photosensitive resin composition was uniformly applied to a polyethylene terephthalate film (GR-16, haze value 2.7%, manufactured by Dinop DuPont film Co., Ltd.) having a thickness of 16 μm as a support by using a bar coater, and then heated and dried in a dryer adjusted to 95 ℃ for 3 minutes and 20 seconds to form a photosensitive resin layer having a thickness of 33 μm on the support.
Next, a polyethylene film (GF-18 manufactured by tamapol co., ltd.) having a thickness of 19 μm as a protective layer was attached to the surface of the photosensitive resin layer opposite to the support, thereby obtaining a photosensitive element.
< substrate used in evaluation >
As the substrate for evaluation, a substrate obtained by surface conditioning the surface of a 1.6mm thick copper-clad laminate laminated with a 35 μm rolled copper foil by wet polishing with a polishing roll was used. The polishing was performed by 2 passes using a saki (registered trademark) HD #600 manufactured by 3M company.
< lamination >
The polyethylene films of the photosensitive elements obtained in examples and comparative examples were peeled off from the surface-conditioned substrate, and laminated in a hot roll laminator (AL-70, manufactured by asahi chemicals) at a roll temperature of 105 ℃, an air pressure of 0.35MPa, and a lamination speed of 1.5 m/min.
< Exposure >
Using a direct write exposure machine (manufactured by Hitachi Via Mechanics Co., Ltd., DE-1AH, light source: GaN blue-violet diode, dominant wavelength 405. + -.5 nm), a mask pattern for DI exposure was formed at an illuminance of 15mW/cm2Is exposed to light under the conditions of (1).
The exposure pattern and the exposure amount are explained later in the items of the respective evaluation items.
< development >
After the support was peeled from the exposed photosensitive resin layer, 0.8 mass% Na at 29 ℃ was sprayed for a time 2 times as long as the minimum development time using an alkali developing machine (FUJI KIKOU co., ltd 2CO3And (4) dissolving and removing the unexposed part of the photosensitive resin layer by using the aqueous solution. After the development, the substrate was washed with pure water for the same time as the development time, and was naturally dried without being subjected to warm air drying treatment after the washing with water, thereby obtaining a substrate having a cured film for evaluation.
The minimum developing time is the minimum time required for the unexposed portion of the photosensitive resin layer to be completely dissolved and removed, and varies depending on the concentration or temperature of the developer, the direction of the spray, the spray amount, the pressure, the frequency of vibration, and the like.
Here, the minimum development time is ranked as follows:
o: the minimum development time is more than 30 seconds.
X: the minimum development time is 30 seconds or less.
< evaluation of sensitivity >
For the evaluation of sensitivity, a laminated substrate after 15 minutes had passed after the above-mentioned < lamination > was used.
The laminated substrate was developed by a method described in < development > after directly drawing and exposing a mask pattern of 10 lines having a line/space of 40 μm/40 μm. The resist top width of the obtained resist pattern was measured by an optical microscope, and the exposure amount at which the resist top width became 39 μm was used as the evaluation of sensitivity.
Here, the measurement position of the resist line is a position of the 5 th line from the end among the 10 lines and about 5mm from the end in the longitudinal direction, and an average value of 3 measurements is used as the measurement value. The line width is different between the end portion and the central portion of the pattern due to the influence of the diffusion of the developer and the cleaning water, and the resist line on the end portion side tends to be thin, so that it is important to define the measurement position.
The exposure dose in the following evaluation items is an exposure dose in which the resist top width is 39 μm for a mask pattern having a line/space of 40 μm/40 μm as described in the above < evaluation of sensitivity >. Here, the sensitivity is ranked according to the exposure amount as follows:
o: the exposure dose to a line width of 39 μm was 28mJ/cm2The following.
X: the exposure dose for reaching 39 μm line width exceeds 28mJ/cm2。
< evaluation of resolution >
For the evaluation of the resolution, a laminated substrate after 15 minutes had passed after the above-mentioned < lamination > was used.
The laminated substrate was developed by the method described in < development > after directly drawing and exposing patterns of various sizes of line/space 1/1.
The minimum pattern width formed was observed with an optical microscope for the obtained pattern, and the resolution was evaluated according to the following criteria.
O: the minimum pattern width formed is 28 μm or less.
X: the minimum pattern width formed exceeds 28 μm.
< evaluation of adhesion >
For evaluation of adhesion, a laminated substrate after 15 minutes had passed after the above-mentioned < lamination > was used.
The laminated substrate was developed by the method described in < development > after directly drawing and exposing the pattern of the individual lines of various sizes.
The obtained pattern was observed with an optical microscope, and the adhesion was evaluated according to the following criteria.
Here, the case where the line pattern is not normally formed means a case where the line pattern collapses, a case where the line pattern meanders, or a case where the line pattern is not present on the substrate.
O: the minimum pattern width formed is 28 μm or less.
X: the minimum pattern width formed exceeds 28 μm.
< evaluation of aggregability >
The photopolymerizable resin laminate was 50 μm thick and 0.6m in area2The photosensitive layer (resist) of (2) was dissolved in 200ml of 1 mass% Na2CO3The aqueous solution was sprayed at a spray pressure of 0.1MPa for 3 hours by using a circulating spray apparatus. Then, the developer was allowed to stand for 1 day, and generation of aggregates was observed. When the aggregates were produced in large quantities, powders or oils were observed at the bottom and side of the spray device. In the composition having a good developer aggregating property, the above aggregate is not generated at all. Based on the state of aggregate production, the aggregability is ranked as follows:
O: no aggregates were produced at all.
And (delta): aggregates are observed in a part of the bottom or side of the spraying device.
X: aggregates were observed throughout the spray device.
< evaluation of peelability >
Using the substrate after 15 minutes from the treatment described in < lamination >, a rectangular pattern of 4cm × 6cm was directly drawn and exposed on the laminated substrate, and then developed by the method described in < development >.
The cured resist on the substrate obtained was immersed in 3 mass% NaOH at 50 ℃, and the time until the resist was completely peeled from the substrate was measured as the peeling time.
Here, the peelability was rated as follows:
o: the time required for complete peeling is 40 seconds or less.
X: the time until complete peeling exceeded 40 seconds.
Examples 1 to 7 and comparative examples 1 to 4
Table 8 shows the compositions of the photosensitive resin compositions used in examples and comparative examples, and table 9 shows the details of the component names shown in table 8. The blending amounts of the respective components in table 8 are all parts by mass in terms of solid content.
The results of the evaluations using the respective compositions are also shown in table 8.
Figure BDA0003379849860001141
TABLE 9
Figure BDA0003379849860001151

Claims (28)

1. A photosensitive resin composition comprising:
(A) An alkali-soluble polymer;
(B) a compound containing an ethylenically unsaturated bond; and
(C) a photopolymerization initiator;
the alkali-soluble polymer (A) contains a first copolymer having a content ratio of acid monomer units of 10 to less than 25 mass% and a content ratio of aromatic monomer units of 30 to 60 mass%, and,
the weight average molecular weight of the ethylenically unsaturated bond-containing compound (B) is 50-900.
2. The photosensitive resin composition according to claim 1, wherein the (C) photopolymerization initiator comprises an acridine compound.
3. The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble polymer (a) comprises a second copolymer having a content ratio of an aromatic monomer unit of 45 to 90% by mass.
4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the ethylenically unsaturated bond-containing compound (B) comprises a tri (meth) acrylate compound represented by the following general formula (III),
Figure FDA0003379849850000011
in the formula (III), R5、R6And R7Independently represents a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m2、m3And m4Independently of one another, m is an integer of 0 to 402+m3+m40 to 40 and m 2+m3+m4In the case of 2 or more, a plurality of xs may be the same as or different from each other.
5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the ethylenically unsaturated bond-containing compound (B) comprises an alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the following general formula (II),
Figure FDA0003379849850000021
in the formula (II), R3And R4Independently of one another, represents a hydrogen atom or a methyl group, A is C2H4B is C3H6，n1、n2、n3And n4To satisfy n1+n2+n3+n4The arrangement of the repeating units of- (a-O) -and- (B-O) -may be random or block, and in the case of a block, any one of- (a-O) -and- (B-O) -may be optionally on the biphenyl side.
6. The photosensitive resin composition according to any one of claims 1 to 5, further comprising a compound represented by the following general formula (V) as a hindered phenol,
Figure FDA0003379849850000022
in the formula (V), R51Represents an optionally substituted, straight-chain alkyl group, branched-chain alkyl group, aryl group, cyclohexyl group, straight-chain alkyl group sandwiching a divalent linking group, branched-chain alkyl group sandwiching a divalent linking group, cyclohexyl group sandwiching a divalent linking group, or aryl group sandwiching a divalent linking group, and R52、R53And R54Each independently represents hydrogen, or an optionally substituted, straight-chain alkyl group, branched-chain alkyl group, aryl group, cyclohexyl group, straight-chain alkyl group sandwiching a divalent linking group, branched-chain alkyl group sandwiching a divalent linking group, cyclohexyl group sandwiching a divalent linking group, or aryl group sandwiching a divalent linking group.
7. The photosensitive resin composition according to any one of claims 1 to 6, which is used for direct image-wise exposure.
8. A photosensitive element obtained by laminating a photosensitive resin layer formed from the photosensitive resin composition according to any one of claims 1 to 7 on a support.
9. A method of forming a resist pattern, comprising:
a laminating step of laminating the photosensitive resin layer of the photosensitive element according to claim 8 on a conductor substrate;
an exposure step of exposing the laminated photosensitive resin layer; and
and a developing step of developing the exposed photosensitive resin layer.
10. A method of manufacturing a circuit board, comprising:
a laminating step of laminating the photosensitive resin layer of the photosensitive element according to claim 8 on a conductor substrate;
an exposure step of exposing the laminated photosensitive resin layer;
a developing step of developing the exposed photosensitive resin layer to form a resist pattern on the conductor substrate;
a conductor pattern forming step of etching or plating the conductor substrate on which the resist pattern is formed; and
and a peeling step of peeling off the resist pattern.
11. A photosensitive resin composition, comprising:
(A) an alkali-soluble polymer;
(B) a compound containing an ethylenically unsaturated bond; and
(C) a photopolymerization initiator;
the alkali-soluble polymer (A) contains 10 to 24 mass% of a structural unit of (meth) acrylic acid and 35 to 90 mass% of a structural unit of styrene based on the total mass of monomers constituting the alkali-soluble polymer (A),
the weight average molecular weight of the ethylenically unsaturated bond-containing compound (B) is 1200-5000.
12. The photosensitive resin composition according to claim 11, wherein the weight average molecular weight of the ethylenically unsaturated bond-containing compound (B) is 1300 or more.
13. The photosensitive resin composition according to claim 11 or 12, wherein 40% by mass or more of the ethylenically unsaturated bond-containing compound (B) is an alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the following general formula (II),
Figure FDA0003379849850000041
in the formula (II), R3And R4Independently of one another, represents a hydrogen atom or a methyl group, A is C2H4B is C3H6，n1、n2、n3And n4To satisfy n1+n2+n3+n4The arrangement of the repeating units of- (a-O) -and- (B-O) -may be random or block, and in the case of a block, any one of- (a-O) -and- (B-O) -may be optionally on the biphenyl side.
14. The photosensitive resin composition according to claim 13, wherein n in the general formula (II)1、n2、n3And n4Satisfies n1+n2+n3+n4The relationship is 30 to 50.
15. The photosensitive resin composition according to claim 13, wherein n in the general formula (II)1、n2、n3And n4Satisfies n1+n2+n3+n4The relationship is 2-10.
16. The photosensitive resin composition according to claim 11 or 12, wherein the ethylenically unsaturated bond-containing compound (B) comprises a tri (meth) acrylate compound represented by the following general formula (III),
Figure FDA0003379849850000051
in the formula (III), R5、R6And R7Independently represents a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m2、m3And m4Independently of one another, m is an integer of 0 to 402+m3+m41 to 40, and m2+m3+m4In the case of 2 or more, a plurality of xs may be the same as or different from each other.
17. The photosensitive resin composition according to claim 11 or 12, wherein the ethylenically unsaturated bond-containing compound (B) comprises a urethane di (meth) acrylate compound represented by the following general formula (IV),
Figure FDA0003379849850000052
in the formula (IV), R8And R9Independently represents a hydrogen atom or a methyl group, Y represents an alkylene group having 2 to 6 carbon atoms, Z represents a divalent organic group, s and t are independently integers of 0 to 40, and s + t.gtoreq.1.
18. The photosensitive resin composition according to any one of claims 11 to 17, wherein the alkali-soluble polymer (a) further comprises a structural unit of butyl (meth) acrylate.
19. The photosensitive resin composition according to any one of claims 11 to 18, which is used for direct image-wise exposure.
20. A method of forming a resist pattern, comprising:
a laminating step of laminating a photosensitive resin layer formed from the photosensitive resin composition according to any one of claims 11 to 19 on a support;
an exposure step of exposing the photosensitive resin layer; and
and a developing step of developing the exposed photosensitive resin layer.
21. A method of manufacturing a circuit board, comprising:
a laminating step of laminating a photosensitive resin layer formed from the photosensitive resin composition according to any one of claims 11 to 19 on a substrate;
an exposure step of exposing the photosensitive resin layer;
a developing step of developing the exposed photosensitive resin layer to obtain a substrate on which a resist pattern is formed;
a conductor pattern forming step of etching or plating the substrate on which the resist pattern is formed; and
a stripping step of stripping the resist pattern.
22. A photosensitive resin composition comprising the following components (A) to (C),
(A) the components: an alkali-soluble polymer having an acid equivalent of 100 to 600,
(B) The components: a compound having an olefinic double bond, and
(C) the components: photopolymerization initiator
The component (A) contains a copolymer containing 50 to 80 mass% of a styrene unit,
the component (B) contains a compound represented by the following general formula (I),
Figure FDA0003379849850000061
in the formula (I), R is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n1, n2 and n3 are independently integers of 0 to 30, wherein the condition that n1+ n2+ n3 is not less than 6 is satisfied,
the content of the compound represented by the general formula (I) is 5 to 30 mass% relative to the solid content of the photosensitive resin composition, and the component (C) contains an acridine compound.
23. The photosensitive resin composition according to claim 22, wherein n1, n2 and n3 in the general formula (I) satisfy 20. gtoreq.n 1+ n2+ n3 > 9.
24. The photosensitive resin composition according to claim 22 or 23, wherein all of R in the general formula (I) are hydrogen atoms.
25. The photosensitive resin composition according to any one of claims 22 to 24, wherein the component (B) further contains a pentaerythritol-modified monomer.
26. A photosensitive element obtained by laminating a photosensitive resin layer formed from the photosensitive resin composition according to any one of claims 22 to 25 on a support.
27. A method of forming a resist pattern, comprising:
a laminating step of laminating the photosensitive resin layer of the photosensitive element according to claim 26 on a conductor substrate,
An exposure step of exposing the laminated photosensitive resin layer, and
and a developing step of removing the unexposed portion with a developing solution.
28. A method of manufacturing a circuit board, comprising:
a laminating step of laminating the photosensitive resin layer of the photosensitive element according to claim 26 on a conductor substrate,
An exposure step of exposing the laminated photosensitive resin layer,
A developing step of removing the unexposed portion with a developing solution,
A conductor pattern forming step of etching or plating the conductor substrate on which the resist pattern is formed by the development, and
and a peeling step of peeling off the resist pattern.
CN202111430178.6A 2015-09-11 2016-09-07 Photosensitive resin composition Pending CN114296315A (en)

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